U.S. patent application number 13/833828 was filed with the patent office on 2013-10-17 for controlled radical polymerization initiators.
The applicant listed for this patent is PPG INDUSTRIES OHIO, INC.. Invention is credited to Charles R. Hickenboth, Matthew J. Kryger, Cynthia Kutchiko.
Application Number | 20130273380 13/833828 |
Document ID | / |
Family ID | 49325379 |
Filed Date | 2013-10-17 |
United States Patent
Application |
20130273380 |
Kind Code |
A1 |
Hickenboth; Charles R. ; et
al. |
October 17, 2013 |
CONTROLLED RADICAL POLYMERIZATION INITIATORS
Abstract
The present invention relates to controlled radical
polymerization (CRP) initiators that include at least one radically
transferable group. The CRP initiators include at least one of the
following, (a) a spirooxazine compound represented by the following
Formula (I), ##STR00001## and (b) an indenonaphthopyran represented
by the following Formula (II), ##STR00002## One or more of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 of the
spirooxazine, and one or more of R.sub.7, R.sub.8, R.sub.9,
R.sub.10, B, and B' independently include the radically
transferable group. The present invention also relates to polymers,
such as mechanochromic polymers, that are prepared from such CRP
initiators, polymer compositions that include such polymers, and
mechanochromic articles that include such polymer compositions.
Inventors: |
Hickenboth; Charles R.;
(Cranberry Township, PA) ; Kutchiko; Cynthia;
(Pittsburgh, PA) ; Kryger; Matthew J.;
(Pittsburgh, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
PPG INDUSTRIES OHIO, INC. |
Cleveland |
OH |
US |
|
|
Family ID: |
49325379 |
Appl. No.: |
13/833828 |
Filed: |
March 15, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13447604 |
Apr 16, 2012 |
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13833828 |
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Current U.S.
Class: |
428/446 ;
428/704; 524/559; 524/560; 525/330.3; 525/330.4; 525/330.5;
526/328.5; 526/329.7; 544/71; 546/187; 546/196; 549/382 |
Current CPC
Class: |
C08L 33/08 20130101;
C08F 20/10 20130101; G03C 1/733 20130101; C08G 18/72 20130101; C08F
4/32 20130101 |
Class at
Publication: |
428/446 ;
526/329.7; 526/328.5; 525/330.3; 525/330.4; 525/330.5; 524/559;
524/560; 549/382; 544/71; 546/196; 546/187; 428/704 |
International
Class: |
C08F 4/32 20060101
C08F004/32; C08L 33/08 20060101 C08L033/08; C08F 20/10 20060101
C08F020/10 |
Claims
1. A controlled radical polymerization initiator comprising at
least one radically transferable group, wherein said controlled
radical polymerization initiator comprises at least one of, (a) a
spirooxazine compound represented by the following Formula (I),
##STR00024## wherein n is from 1 to 4, p is from 1 to 2, q is from
1 to 4, and R.sub.1 independently for each n, R.sub.2 independently
for each p, R.sub.3 independently for each q, R.sub.4, R.sub.5, and
R.sub.6 are each independently selected from hydrogen, hydrocarbyl
and substituted hydrocarbyl each optionally interrupted with at
least one of --O--, --S--,--C(O)--, --C(O)O--, --OC(O)O--,
--S(O)--, --SO.sub.2--, --N(R.sup.11)--, and
--Si(R.sup.11)(R.sup.12)-- wherein R.sup.11 and R.sup.12 are each
independently selected from hydrogen, hydrocarbyl and substituted
hydrocarbyl, and combinations of two or more thereof, provided that
for the spirooxazine represented by Formula (I) at least one of
R.sub.1 independently for each n, R.sub.2 independently for each p,
R.sub.3 independently for each q, R.sub.4, R.sub.5, and R.sub.6,
independently comprise said radically transferable group, and (b)
an indenonaphthopyran represented by the following Formula (II),
##STR00025## wherein x is from 1 to 4, y is from 1 to 4, R.sub.7
independently for each x, R.sub.8 independently for each y,
R.sub.9, and R.sub.10 are each independently selected from
hydrogen, hydrocarbyl and substituted hydrocarbyl each optionally
interrupted with at least one of --O--, --S--, --C(O)--, --C(O)O--,
--OC(O)O--, --S(O)--, --SO.sub.2--, --N(R.sup.11)--, and
--Si(R.sup.11)(R.sup.12)-- wherein R.sup.11 and R.sup.12 are each
independently selected from hydrogen, hydrocarbyl and substituted
hydrocarbyl, and combinations of two or more thereof, and B and B'
are each independently selected from unsubstituted aryl,
substituted aryl, unsubstituted heteroaryl, substituted heteroaryl,
and polyalkoxy, or B and B' taken together form a ring structure
selected from unsubstituted fluoren-9-ylidene, substituted
fluoren-9-ylidene, saturated spiro-monocyclic hydrocarbon ring,
saturated spiro-bicyclic hydrocarbon ring, and spiro-tricyclic
hydrocarbon ring, provided that for the indenonaphthopyran
represented by Formula (II) at least one of R.sub.7 independently
for each x, R.sub.8 independently for each y, R.sub.9, R.sub.10, B,
and B', independently comprise said radically transferable
group.
2. The controlled radical polymerization initiator of claim 1,
wherein for the spirooxazine represented by Formula (I) at least
two of, R.sub.1 independently for each n, R.sub.2 independently for
each p, R.sub.3 independently for each q, R.sub.4, R.sub.5, and
R.sub.6 independently comprise said radically transferable group,
and wherein for the indenonaphthopyran represented by Formula (II)
at least two of, R.sub.7 independently for each x, R.sub.8
independently for each y, R.sub.9, R.sub.10, B, and B'
independently comprise said radically transferable group.
3. The controlled radical polymerization initiator of claim 1,
wherein the spirooxazine represented by Formula (I) comprises at
least one first radically transferable group, and at least one
second radically transferrable group, further wherein for the
spirooxazine represented by Formula (I) at least one of R.sub.11
independently for each n, and R.sub.2 independently for each p,
independently comprise said first radically transferable group, and
at least one of R.sub.3 independently for each q, R.sub.4, R.sub.5
and R.sub.6 independently comprise said second radically
transferable group, and wherein the indenonaphthopyran represented
by Formula (II) comprises at least one first radically transferable
group, and at least one second radically transferrable group,
further wherein for the indenonaphthopyran represented by Formula
(II) at least one of B and B' independently comprise said first
radically transferable group, and at least one of R.sub.7
independently for each x, R.sub.3 independently for each y, R.sub.9
and R.sub.10 independently comprise said second radically
transferable group.
4. The controlled radical polymerization initiator of claim 1,
wherein the spirooxazine represented by Formula (I) comprises one
first radically transferable group, and one second radically
transferrable group, further wherein for the spirooxazine
represented by Formula (I) one of R.sub.1 and R.sub.2 comprises
said first radically transferable group, and one of R.sub.3,
R.sub.4, R.sub.5, and R.sub.6 comprises said second radically
transferable group, and wherein the indenonaphthopyran represented
by Formula (II) comprises one first radically transferable group,
and one second radically transferrable group, further wherein for
the indenonaphthopyran represented by Formula (II) one of B and B'
comprises said first radically transferable group, and one of
R.sub.7, R.sub.8, R.sub.9, and R.sub.10 comprises said second
radically transferable group.
5. The controlled radical polymerization initiator of claim 3,
wherein the spirooxazine represented by Formula (I) comprises one
first radically transferable group, and one second radically
transferrable group, further wherein for the spirooxazine
represented by Formula (I) one R.sub.2 comprises said first
radically transferable group, and one R.sub.3 comprises said second
radically transferable group, and wherein the indenonaphthopyran
represented by Formula (II) comprises one first radically
transferable group, and one second radically transferrable group,
further wherein for the indenonaphthopyran represented by Formula
(II) one of B and B' comprises said first radically transferable
group, and one of R.sub.7 and R.sub.8 comprises said second
radically transferable group.
6. The controlled radical polymerization initiator of claim 1,
wherein said radically transferable group is a halo group selected
from Cl, Br and I.
7. The controlled radical polymerization initiator of claim 1
wherein, for the spirooxazine represented by Formula (I) at least
one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6
independently comprise a group represented by the following Formula
(III), and for the indenonaphthopyran represented by Formula (II)
at least one of R.sub.7, R.sub.8, R.sub.9, R.sub.10, B, and B' case
independently comprise said group represented by the following
Formula (III), ##STR00026## wherein R.sub.13 is a divalent linking
group selected from a bond, a divalent hydrocarbyl group and a
divalent substituted hydrocarbyl group each optionally interrupted
with at least one of --O--, --S--, --C(O)--, --C(O)O--, --OC(O)O--,
--S(O)--, --SO.sub.2--, --N(R.sup.15)-- and
--Si(R.sup.15)(R.sup.16)-- and combinations of two or more thereof,
wherein R.sup.15 and R.sup.16 are in each case independently
selected from hydrogen, hydrocarbyl and substituted hydrocarbyl,
and R.sub.14 is a divalent linking group selected from a bond,
divalent hydrocarbyl, and divalent substituted hydrocarbyl, and X
is said radically transferrable group.
8. The controlled radical polymerization initiator of claim 7,
wherein R.sub.13 is selected from a bond, divalent C.sub.1-C.sub.20
linear or branched alkyl, divalent C.sub.3-C.sub.10 cyclic alkyl,
divalent C.sub.3-C.sub.10 heterocyclic alkyl, divalent aryl,
divalent heteroaryl, and combinations thereof optionally
interrupted with at least one of --O-- and --S-- and combinations
of two or more thereof. R.sub.14 is selected from divalent
C.sub.1-C.sub.20 linear or branched alkyl, and X is selected from a
halo group.
9. The controlled radical polymerization initiator of claim 8,
wherein R.sub.13 is selected from a bond, divalent C.sub.1-C.sub.10
linear or branched alkyl, divalent C.sub.3-C.sub.10 heterocyclic
alkyl, divalent aryl, and combinations thereof optionally
interrupted with at least one of --O--, R.sub.14 is selected from
divalent C.sub.1-C.sub.10 linear or branched alkyl, and said halo
group from which X is selected is Cl, Br, or I.
10. The controlled radical polymerization initiator of claim 7
wherein, for the spirooxazine represented by Formula (I), one
R.sub.2 independently comprises said group represented by Formula
(III), and one R.sub.3 independently comprises said group
represented by Formula (II), and for the indenonaphthopyran
represented by Formula (II), one of B and B' independently
comprises said group represented by Formula (III), and one of
R.sub.7 and R.sub.8 independently comprises said group represented
by Formula (III).
11. The controlled radical polymerization initiator of claim 1
wherein, for the spirooxazine compound represented by Formula (I),
R.sub.1 independently for each n and R.sub.2 independently for each
p are each independently selected from hydrogen, aryl,
mono(C.sub.1-C.sub.6)alkoxyaryl, di(C.sub.1-C.sub.6)alkoxyaryl,
mono(C.sub.1-C.sub.6)alkylaryl, di(C.sub.1-C.sub.8)alkylaryl,
bromoaryl, chloroaryl, fluoroaryl, C.sub.3-C.sub.7 cycloalkylaryl,
C.sub.3-C.sub.7 cycloalkyl, C.sub.3-C.sub.7 cycloalkyloxy,
C.sub.3-C.sub.7 cycloalkyloxy(C.sub.1-C.sub.8)alkyl,
C.sub.3-C.sub.7 cycloalkyloxy(C.sub.1-C.sub.6)alkoxy,
aryl(C.sub.1-C.sub.6)alkyl, aryl(C.sub.1-C.sub.6)alkoxy, aryloxy,
aryloxy(C.sub.1-C.sub.6)alkyl, aryloxy(C.sub.1-C.sub.6)alkoxy,
mono- or di(C.sub.1-C.sub.6)alkylaryl(C.sub.1-C.sub.6)alkyl, mono-
or di(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub.6)alkyl, mono- or
di(C.sub.1-C.sub.6)alkylaryl(C.sub.1-C.sub.6)alkoxy, mono- or
di(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub.6)alkoxy, amino,
mono(C.sub.1-C.sub.6)alkylamino, di(C.sub.1-C.sub.6)alkylamino,
diarylamino, N--(C.sub.1-C.sub.6)alkylpiperazino, N-arylpiperazino,
aziridino, indolino, piperidino, arylpiperidino, morpholino,
thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino,
pyrryl, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 bromoalkyl,
C.sub.1-.sub.C6 chloroalkyl, C.sub.1-C.sub.6 fluoroalkyl,
C.sub.1-C.sub.6 alkoxy,
mono(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.4)alkyl, acryloxy,
methacryloxy, acyloxy(C.sub.1-C.sub.6 alkyl),
acyloxy(C.sub.3-C.sub.7 cycloalkyl), acyloxy(aryl), bromo, chloro
or fluoro, R.sub.3 is, independently for each q, chosen from
hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy, nitro,
cyano, C.sub.1-C.sub.8 alkoxycarbonyl, acyloxy(C.sub.1-C.sub.8
alkyl), acyloxy(C.sub.3-C.sub.7 cycloalkyl), acyloxy(aryl),, halo,
C.sub.1-C.sub.4 monohaloalkyl or C.sub.1-C.sub.4 polyhaloalkyl;
said halo substituents being chloro, fluoro, iodo or bromo, R.sub.4
is chosen from hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.3-C.sub.7
cycloalkyl, phen(C.sub.1-C.sub.4)alkyl,
naphth(C.sub.1-C.sub.4)alkyl, allyl,
acrylyloxy(C.sub.2-C.sub.6)alkyl,
methacrylyloxy(C.sub.2-C.sub.6)alkyl, C.sub.2-C.sub.4
acyloxy(C.sub.2-C.sub.6)alkyl, carboxy(C.sub.2-C.sub.6)alkyl,
cyano(C.sub.2-C.sub.6)alkyl, hydroxy(C.sub.2-C.sub.6)alkyl,
triarylsilyl, triarylsilyloxy, tri(C.sub.1-C.sub.6)alkylsilyl,
tri(C.sub.1-C.sub.6)alkylsilyloxy, tri(C.sub.1-C.sub.6)alkoxysilyl,
tri(C.sub.1-C.sub.6)alkoxysilyloxy,
di(C.sub.1-C.sub.6)alkyl(C.sub.1-C.sub.6 alkoxy)silyl,
di(C.sub.1-C.sub.6)alkyl(C.sub.1-C.sub.6 alkoxy)silyloxy,
di(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6 alkyl)silyl,
di(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6 alkyl)silyloxy,
C.sub.1-C.sub.6 alkoxy(C.sub.2-C.sub.4)alkyl or
(C.sub.2H.sub.4O).sub.rCH.sub.3, wherein r is an integer from 1 to
6, R.sub.5 and R.sub.6 are each independently selected from
hydrogen, C.sub.1-C.sub.5 alkyl, acyloxy(C.sub.1-C.sub.6 alkyl),
acyloxy(C.sub.3-C.sub.7 cycloalkyl), acyloxy(aryl), benzyl, phenyl,
mono- or di-substituted phenyl, said phenyl substituents being
C.sub.1-C.sub.5 alkyl or C.sub.1-C.sub.5 alkoxy; or R.sub.5 and
R.sub.6 taken together form a group chosen from a cyclic ring of
from 5 to 8 carbon atoms which includes the spiro carbon atom, for
the indenonaphthopyran represented by Formula (II), R.sub.7
independently for each x and R.sub.8 independently for each y are
each independently selected from, hydrogen; a compatiblizing
substituent; halogen selected from fluoro and chloro;
C.sub.1-C.sub.20 alkyl; C.sub.3-C.sub.10 cycloalkyl;
acyloxy(C.sub.1-C.sub.6 alkyl), acyloxy(C.sub.3-C.sub.7
cycloalkyl), acyloxy(aryl); substituted or unsubstituted phenyl,
the phenyl substituents being selected from hydroxyl, halogen,
carbonyl, C.sub.1-C.sub.20 alkoxycarbonyl, cyano,
halo(C.sub.1-C.sub.20)alkyl, C.sub.1-C.sub.20 alkyl or
C.sub.1-C.sub.20 alkoxy; --O--R.sub.10' or --C(O)--R.sub.10' or
--C(O)--OR.sub.10', wherein R.sub.10' is hydrogen, C.sub.1-C.sub.20
alkyl, phenyl(C.sub.1-C.sub.20)alkyl, mono(C.sub.1-C.sub.20)alkyl
substituted phenyl(C.sub.1-C.sub.20)alkyl,
mono(C.sub.1-C.sub.20)alkoxy substituted
phenyl(C.sub.1-C.sub.20)alkyl,
(C.sub.1-C.sub.20)alkoxy(C.sub.2-C.sub.20)alkyl, C.sub.3-C.sub.10
cycloalkyl, or mono(C.sub.1-C.sub.20)alkyl substituted
C.sub.3-C.sub.10 cycloalkyl; --N(R.sub.11')R.sub.12', wherein
R.sub.11' and R.sub.12' are each independently hydrogen,
C.sub.1-C.sub.20 alkyl, phenyl, naphthyl, furanyl, benzofuran-2-yl,
benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl,
dibenzofuranyl, dibenzothienyl, benzopyridyl, fluorenyl,
C.sub.1-C.sub.20 alkylaryl, C.sub.3-C.sub.10 cycloalkyl,
C.sub.4-C.sub.20 bicycloalkyl, C.sub.5-C.sub.20 tricycloalkyl or
C.sub.1-C.sub.20 alkoxyalkyl, wherein said aryl group is phenyl or
naphthyl, or R.sub.11' and R.sub.12' come together with the
nitrogen atom to form a C.sub.3-C.sub.20 hetero-bicycloalkyl ring
or a C.sub.4-C.sub.20 hetero-tricycloalkyl ring; a nitrogen
containing ring represented by the following graphic formula IVA,
##STR00027## wherein each --Y-- is independently chosen for each
occurrence from --CH.sub.2--, --CH(R.sub.13')--,
--C(R.sub.13').sub.2--, --CH(aryl)-, --C(aryl).sub.2-, and
--C(R.sub.13')(aryl)-, and Z is --Y--, --O--, --S--, --S(O)--,
--SO.sub.2--, --NH--, --N(R.sub.13')--, or --N(aryl)-, wherein each
R.sub.13' is independently C.sub.1-C.sub.20 alkyl, each aryl is
independently phenyl or naphthyl, m is an integer 1, 2 or 3, and p
is an integer 0, 1, 2, or 3 and provided that when p is 0, Z is
--Y--; a group represented by one of the following graphic formulas
IVB or IVC, ##STR00028## wherein R.sub.15, R.sub.16, and R.sub.17
are each independently hydrogen, C.sub.1-C.sub.6 alkyl, phenyl, or
naphthyl, or the groups R.sub.15 and R.sub.16 together form a ring
of 5 to 8 carbon atoms and each Rd is independently for each
occurrence selected from C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20
alkoxy, fluoro or chloro, and Q is an integer 0, 1, 2, or 3; and
unsubstituted, mono-, or di-substituted C.sub.4-C.sub.18
spirobicyclic amine, or unsubstituted, mono-, and di-substituted
C.sub.4-C.sub.18 spirotricyclic amine, wherein said substituents
are independently aryl, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20
alkoxy, or phenyl(C.sub.1-C.sub.20)alkyl; or two adjacent R.sub.7
groups, or two adjacent R.sub.8 groups, independently together form
a group represented by one of IVD and IVE: ##STR00029## wherein T
and T' are each independently oxygen or the group --NR.sub.11'--,
where R.sub.11', R.sub.15, and R.sub.16 are as set forth above,
R.sub.9 and R.sub.10 are each independently selected from, (i)
hydrogen, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 haloalkyl,
C.sub.3-C.sub.10 cycloalkyl, acyloxy(C.sub.1-C.sub.6alkyl),
acyloxy(C.sub.3-C.sub.7 cycloalkyl), acyloxy(aryl), allyl, benzyl,
or mono-substituted benzyl, said benzyl substituents being chosen
from halogen, C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20 alkoxy;
(ii) an unsubstituted, mono- di- or tri-substituted group chosen
from phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl,
benzofuranyl, thienyl, benzothienyl, dibenzofuranyl,
dibenzothienyl, carbazolyl, or indolyl, said group substituents in
each case being independently chosen from halogen, C.sub.1-C.sub.20
alkyl or C.sub.1-C.sub.20 alkoxy; (iii) mono-substituted phenyl,
said substituent located at the para position being
--(CH.sub.2).sub.t-- or --O--(CH.sub.2).sub.t--, wherein t is the
integer 1, 2, 3, 4, 5 or 6, said substituent being connected to an
aryl group which is a member of a photochromic material; (iv) the
group --CH(R.sup.18)G, wherein R.sup.18 is hydrogen,
C.sub.1-C.sub.6 alkyl or the unsubstituted, mono- or di-substituted
aryl groups phenyl or naphthyl, and G is --CH.sub.2OR.sup.19,
wherein R.sup.19 is hydrogen, --C(O)R.sup.10, C.sub.1-C.sub.20
alkyl, C.sub.1-C.sub.20 alkoxy(C.sub.1-C.sub.20)alkyl,
phenyl(C.sub.1-C.sub.20)alkyl, mono(C.sub.1-C.sub.20)alkoxy
substituted phenyl(C.sub.1-C.sub.20)alkyl, or the unsubstituted,
mono- or di-substituted aryl groups phenyl or naphthyl, each of
said phenyl and naphthyl group substituents being C.sub.1-C.sub.20
alkyl or C.sub.1-C.sub.20 alkoxy; or (v) R.sub.9 and R.sub.10
together form a spiro substituent selected from a substituted or
unsubstituted spiro-carbocyclic ring containing 3 to 6 carbon
atoms, a substituted or unsubstituted spiro-heterocyclic ring
containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including
the spirocarbon atom, said spiro-carbocyclic ring and
spiro-heterocyclic ring being annellated with 0, 1 or 2 benzene
rings, said substituents being hydrogen or C.sub.1-C.sub.20 alkyl;
and B and B' are each independently: an aryl group that is
mono-substituted with a compatiblizing substituent; a substituted
phenyl; a substituted aryl; a substituted 9-julolindinyl; a
substituted heteroaromatic group chosen from pyridyl, furanyl,
benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,
benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl,
benzopyridyl, indolinyl, and fluorenyl, wherein the phenyl, aryl,
9-julolindinyl, or heteroaromatic substituent is a reactive
substituent R; an unsubstituted, mono-, di-, or tri-substituted
phenyl or aryl group; 9-julolidinyl; or an unsubstituted, mono- or
di-substituted heteroaromatic group chosen from pyridyl, furanyl,
benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,
benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl,
benzopyridyl, indolinyl, and fluorenyl, wherein each of the phenyl,
aryl and heteroaromatic substituents are each independently:
hydroxyl, a group --C(.dbd.O)R.sub.21, wherein R.sub.21 is
--OR.sub.2, --N(R.sub.23)R.sub.24, piperidino, or morpholino,
wherein R.sub.22 is allyl, C.sub.1-C.sub.20 alkyl, phenyl,
mono(C.sub.1-C.sub.20)alkyl substituted phenyl,
mono(C.sub.1-C.sub.20)alkoxy substituted phenyl,
phenyl(C.sub.1-C.sub.20)alkyl, mono(C.sub.1-C.sub.20)alkyl
substituted phenyl(C.sub.1-C.sub.20)alkyl,
mono(C.sub.1-C.sub.20)alkoxy substituted
phenyl(C.sub.1-C.sub.20)alkyl, C.sub.1-C.sub.20
alkoxy(C.sub.2-C.sub.20)alkyl or C.sub.1-C.sub.20 haloalkyl,
R.sub.23 and R.sub.24 are each independently C.sub.1-C.sub.20
alkyl, C.sub.5-C.sub.10 cycloalkyl, phenyl or substituted phenyl,
the phenyl substituents being C.sub.1-C.sub.20 alkyl or
C.sub.1-C.sub.20 alkoxy, and said halo substituent is chloro or
fluoro, aryl, mono(C.sub.1-C.sub.20)alkoxyaryl,
di(C.sub.1-C.sub.20)alkoxyaryl, mono(C.sub.1-C.sub.20)alkylaryl,
di(C.sub.1-C.sub.20)alkylaryl, haloaryl, C.sub.3-C.sub.10
cycloalkylaryl, C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10
cycloalkyloxy, C.sub.3-C.sub.10
cycloalkyloxy(C.sub.1-C.sub.20)alkyl, C.sub.3-C.sub.10
cycloalkyloxy(C.sub.1-C.sub.20)alkoxy, aryl(C.sub.1-C.sub.20)alkyl,
aryl(C.sub.1-C.sub.20)alkoxy, aryloxy,
aryloxy(C.sub.1-C.sub.20)alkyl, aryloxy(C.sub.1-C.sub.20)alkoxy,
mono- or di(C.sub.1-C.sub.20)alkylaryl(C.sub.1-C.sub.20)alkyl,
mono- or di-(C.sub.1-C.sub.20)alkoxyaryl(C.sub.1-C.sub.20)alkyl,
mono- or di-(C.sub.1-C.sub.20)alkylaryl(C.sub.1-C.sub.20)alkoxy,
mono- or di-(C.sub.1-C.sub.20)alkoxyaryl(C.sub.1-C.sub.20)alkoxy,
amino, mono- or di-(C.sub.1-C.sub.20)alkylamino, diarylamino,
piperazino, N--(C.sub.1-C.sub.20)alkylpiperazino, N-arylpiperazino,
aziridino, indolino, piperidino, morpholino, thiomorpholino,
tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl,
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 haloalkyl,
C.sub.1-C.sub.20 alkoxy,
mono(C.sub.1-C.sub.20)alkoxy(C.sub.1-C.sub.20)alkyl, acryloxy,
methacryloxy, acyloxy(C.sub.1-C.sub.6 alkyl),
acyloxy(C.sub.3-C.sub.7 cycloalkyl), acyloxy(aryl), or halogen; an
unsubstituted or mono-substituted group chosen from pyrazolyl,
imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl,
phenoxazinyl, phenazinyl, and acridinyl, each of said substituents
being C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, phenyl, or
halogen; a group represented by one of: ##STR00030## wherein K is
--CH-- or --O--, and M is --O-- or substituted nitrogen, provided
that when M is substituted nitrogen, K is --CH.sub.2--, the
substituted nitrogen substituents being hydrogen, C.sub.1-C.sub.20
alkyl, or C.sub.1-C.sub.20 acyl, each R.sub.25 being independently
chosen for each occurrence from C.sub.1-C.sub.20 alkyl,
C.sub.1-C.sub.20 alkoxy, hydroxy, and halogen, R.sub.26 and
R.sub.27 each being independently hydrogen or C.sub.1-C.sub.20
alkyl, and u is an integer ranging from 0 to 2; or a group
represented by: ##STR00031## wherein R.sub.28 is hydrogen or
C.sub.1-C.sub.20 alkyl, and R.sub.29 is an unsubstituted, mono-, or
di-substituted group chosen from naphthyl, phenyl, furanyl, and
thienyl, wherein the substituents are C.sub.1-C.sub.10 alkyl,
C.sub.1-C.sub.20 alkoxy, or halogen; or B and B' taken together
form one of a fluoren-9-ylidene, mono-, or di-substituted
fluoren-9-ylidene, each of said fluoren-9-ylidene substituents
being independently chosen from C.sub.1-C.sub.20 alkyl,
C.sub.1-C.sub.20 alkoxy, and halogen.
12. The controlled radical polymerization initiator of claim 11
wherein, for the spirooxazine compound represented by Formula (I),
R.sub.1 independently for each n and R.sub.2 independently for each
p are each independently selected from hydrogen, aryl,
mono(C.sub.1-C.sub.6)alkoxyaryl, di(C.sub.1-C.sub.6)alkylamino,
piperidino, morpholino, C.sub.1-C.sub.6 alkoxy, or fluoro, R.sub.3
is, independently for each q, selected from hydrogen,
C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy, C.sub.1-C.sub.8
alkoxycarbonyl, acyloxy(C.sub.1-C.sub.6 alkyl),
acyloxy(C.sub.3-C.sub.7 cycloalkyl), acyloxy(aryl),, halo,
C.sub.1-C.sub.4 monohaloalkyl or C.sub.1-C.sub.4 polyhaloalkyl; and
said halo substituents being chloro or fluoro, R.sub.4 is selected
from hydrogen, C.sub.1-C.sub.8 alkyl, phen(C.sub.1-C.sub.4)alkyl,
acrylyloxy(C.sub.2-C.sub.8)alkyl,
methacrylyloxy(C.sub.2-C.sub.6)alkyl,
carboxy(C.sub.2-C.sub.6)alkyl, tri(C.sub.1-C.sub.6)alkylsilyl,
tri(C.sub.1-C.sub.6)alkylsilyloxy, tri(C.sub.1-C.sub.6)alkoxysilyl,
tri(C.sub.1-C.sub.6)alkoxysilyloxy,
di(C.sub.1-C.sub.6)alkyl(C.sub.1-C.sub.6 alkoxy)silyl,
di(C.sub.1-C.sub.6)alkyl(C.sub.1-C.sub.6 alkoxy)silyloxy,
di(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6 alkyl)silyl or
di(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6 alkyl)silyloxy, and
R.sub.5 and R.sub.6 are each independently selected from hydrogen,
C.sub.1-C.sub.5 alkyl, phenyl; or R.sub.5 and R.sub.6 taken
together form a group chosen from a cyclic ring of from 5 to 8
carbon atoms which includes the spiro carbon atom, and for the
indenonaphthopyran represented by Formula (II), R.sub.7
independently for each x and R.sub.8 independently for each y are
each independently selected from, hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.3-C.sub.7 cycloalkyl, morpholino, morpholino substituted with
C.sub.1-C.sub.8 linear or branched alkyl, C.sub.1-C.sub.8
haloalkyl, fluoro, chloro, and --O--R.sub.10', R.sub.9 and R.sub.10
are each independently selected from hydrogen, C.sub.1-C.sub.8
alkyl, C.sub.1-C.sub.8 haloalkyl, and C.sub.3-C.sub.7 cycloalkyl,
or together form a spiro substituent selected from a substituted or
unsubstituted spiro-carbocyclic ring containing 3 to 6 carbon
atoms, and B and B' are each independently selected from aryl, aryl
substituted with C.sub.1-C.sub.6 alkoxy, and aryl substituted with
morpholino.
13. A polymer composition comprising at least one polymer prepared
by controlled radical polymerization initiated in the presence of a
controlled radical polymerization initiator having at least one
radically transferable group, wherein each polymer prepared by
controlled radical polymerization is independently represented by
the following Formula (V), ##STR00032## wherein M independently for
each w is a residue of a monomer, .phi. is a residue of said
controlled radical polymerization initiator that is free of said
radically transferable group, X, independently for each z, is or is
derived from said radically transferable group, w, independently
for each z, is an integer of at least 2, and z is an integer of at
least 1, further wherein said controlled radical polymerization
initiator is selected from, (a) a spirooxazine compound represented
by the following Formula (I), ##STR00033## wherein n is from 1 to
4, p is from 1 to 2, q is from 1 to 4, and R.sub.1 independently
for each n, R.sub.2 independently for each p, R.sub.3 independently
for each q, R.sub.4, R.sub.5, and R.sub.6 are each independently
selected from hydrogen, hydrocarbyl and substituted hydrocarbyl
each optionally interrupted with at least one of --O--, --S--,
--C(O)--, --C(O)O--, --OC(O)O--, --S(O)--, --SO.sub.2--,
--N(R.sup.11)--, and --Si(R.sup.11)(R.sup.12)-- wherein R.sup.11
and R.sup.12 are each independently selected from hydrogen,
hydrocarbyl and substituted hydrocarbyl, and combinations of two or
more thereof, and (b) an indenonaphthopyran represented by the
following Formula (II), ##STR00034## wherein x is from 1 to 4, y is
from 1 to 4, R.sub.7 independently for each x, R.sub.8
independently for each y, R.sub.9, and R.sub.10 are each
independently selected from hydrogen, hydrocarbyl and substituted
hydrocarbyl each optionally interrupted with at least one of --O--,
--S--, --C(O)--, --C(O)O--, --OC(O)O--, --S(O)--, --SO.sub.2--,
--N(R.sup.11)--, and --Si(R.sup.11)(R.sup.12)-- wherein R.sup.11
and R.sup.12 are each independently selected from hydrogen,
hydrocarbyl and substituted hydrocarbyl, and combinations of two or
more thereof, and B and B' are each independently selected from
unsubstituted aryl, substituted aryl, unsubstituted heteroaryl,
substituted heteroaryl, and polyalkoxy, or B and B' taken together
form a ring structure selected from unsubstituted
fluoren-9-ylidene, substituted fluoren-9-ylidene, saturated
spiro-monocyclic hydrocarbon ring, saturated spiro-bicyclic
hydrocarbon ring, and spiro-tricyclic hydrocarbon ring, provided
that for the spirooxazine represented by Formula (I) at least one
of R.sub.1 independently for each n, R.sub.2 independently for each
p, R.sub.3 independently for each q, R.sub.4, R.sub.6, and R.sub.6
independently comprise said radically transferable group, and
provided for the indenonaphthopyran represented by Formula (II) at
least one of R.sub.7 independently for each x, R.sub.8
independently for each y, R.sub.9, R.sub.10, B, and B'
independently comprise said radically transferable group.
14. The polymer composition of claim 13 wherein, z is at least 2,
the spirooxazine represented by Formula (I) comprises at least one
first radically transferable group, and at least one second
radically transferrable group, further wherein for the spirooxazine
represented by Formula (I) at least one of R.sub.1 independently
for each n, and R.sub.2 independently for each p, independently
comprise said first radically transferable group, and at least one
of R.sub.3 independently for each q, R.sub.4, R.sub.5 and R.sub.6
independently comprise said second radically transferable group,
and the indenonaphthopyran represented by Formula (II) comprises at
least one first radically transferable group, and at least one
second radically transferrable group, further wherein for the
indenonaphthopyran represented by Formula (II) at least one of B
and B' independently comprise said first radically transferable
group, and at least one of R.sub.7 independently for each x,
R.sub.8 independently for each y, R.sub.9 and R.sub.10
independently comprise said second radically transferable
group.
15. The polymer composition of claim 13 wherein, z is 2, the
spirooxazine represented by Formula (I) comprises one first
radically transferable group, and one second radically
transferrable group, further wherein for the spirooxazine
represented by Formula (I) one R.sub.2 comprises said first
radically transferable group, and one R.sub.3 comprises said second
radically transferable group, and the indenonaphthopyran
represented by Formula (II) comprises one first radically
transferable group, and one second radically transferrable group,
further wherein for the indenonaphthopyran represented by Formula
(II) one of B and B' comprises said first radically transferable
group, and one R.sub.8 comprises said second radically transferable
group.
16. The polymer composition of claim 13 wherein, for the
spirooxazine represented by Formula (I) at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 comprise a group
represented by the following Formula (III), and for the
indenonaphthopyran represented by Formula (II) at least one of
R.sub.7, R.sub.8, R.sub.9, R.sub.10, B, and B' in each case
independently comprise said group represented by the following
Formula (III), ##STR00035## wherein R.sub.13 is a divalent linking
group selected from a bond, a divalent hydrocarbyl group and a
divalent substituted hydrocarbyl group each optionally interrupted
with at least one of --O--, --S--, --C(O)--, --C(O)O--, --OC(O)O--,
--S(O)--, --SO.sub.2--, --N(R.sup.15)-- and
--Si(R.sup.15)(R.sup.16)-- and combinations of two or more thereof,
wherein R.sup.15 and R.sup.16 are in each case independently
selected from hydrogen, hydrocarbyl and substituted hydrocarbyl,
and R.sub.14 is a divalent linking group selected from a bond,
divalent hydrocarbyl, and divalent substituted hydrocarbyl, and X
is said radically transferrable group.
17. The polymer composition of claim 16, wherein said radically
transferable group is a halo group selected from Cl, Br and I.
18. The polymer composition of claim 13, wherein said polymer
comprises at least one active hydrogen group selected from
hydroxyl, thiol, carboxylic acid, primary amine, and secondary
amine, and said polymer composition further comprises at least one
crosslinking agent comprising at least two functional groups
selected from cyclic carboxylic acid anhydrides, oxiranes,
thiooxiranes, isocyanates, thioisocyanates, cyclic carboxylic acid
esters, cyclic amides, and cyclic carbonates.
19. The polymer composition of claim 13 further comprising an
additive selected from heat stabilizers, light stabilizers, and
combinations thereof.
20. A mechanochromic article comprising the polymer composition of
claim 14, wherein said mechanochromic article is selected from
films, sheets, and 3-dimensional articles.
21. The mechanochromic article of claim 20 wherein said
3-dimensional articles are selected from ophthalmic articles,
display articles, windows, mirrors, protective articles and support
articles.
22. The mechanochromic article of claim 21 wherein said
mechanochromic article is selected from ophthalmic articles, and
said ophthalmic articles are selected from corrective lenses,
non-corrective lenses, contact lenses, and magnifying lenses.
23. The mechanochromic article of claim 21 wherein said
mechanochromic article is selected from display articles, and said
display articles are selected from screens, monitors, and security
elements.
24. The mechanochromic article of claim 21 wherein said
mechanochromic article is selected from protective articles, and
said protective articles are selected from protective lenses,
protective visors, protective headgear, and protective
housings.
25. The mechanochromic article of claim 21 wherein said
mechanochromic article is selected from support articles, and said
support articles are selected from rods, beams, crossarms, and
combinations thereof.
26. The mechanochromic article of claim 20 wherein said
mechanochromic article is selected from 3-dimensional articles, and
each 3-dimensionsal article comprises a coating residing over at
least a portion of at least one surface of each 3-dimensional
article, further wherein said coating comprises said polymer
composition of claim 14.
27. A mechanochromic article comprising the polymer composition of
claim 14 wherein said mechanochromic article further comprises a
coating residing over at least a portion of at least one surface of
said mechanochromic article, said coating being free of said
polymer composition of claim 14, and said coating comprising an
additive selected from heat stabilizers, light stabilizers, and
combinations thereof.
Description
CROSS REFERENCE TO RELATED PATENT APPLICATION
[0001] The present patent application is a continuation in part of
and claims priority to U.S. patent application Ser. No. 13/447,604,
filed on Apr. 16, 2012, the disclosure of which is incorporated
herein in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to controlled radical
polymerization initiators that include a spirooxazine compound or
an indenonaphthopyran compound, polymers and polymer compositions
prepared therefrom, and mechanochromic articles that include such
polymers and/or polymer compositions.
BACKGROUND OF THE INVENTION
[0003] Various articles, such as protective articles and support
articles are typically fabricated at least in part from polymeric
materials. Protective articles, such as helmets, safety lenses, and
protective housings, and support articles, such as beams can be
subjected to stresses and/or impacts that result in damage to the
article, which could lead to catastrophic failure of the article at
a point in time after the damage occurred. In some instances, the
occurrence or presence of such damage is not accompanied by a
visually observable indication thereof in the article. In the
absence of a visually observable indication of the damage, the
damaged article would not likely be withdrawn from use, and an
unexpected catastrophic failure of the article could occur.
[0004] Mechanochromic materials change color in response to a
change in mechanical stress, such as impacts. It is known that
mechanochromic materials can be incorporated into certain articles
so as to provide a visual indication that the article has undergone
a threshold mechanical stress event, which could result in
catastrophic failure thereof. Some mechanochromic materials can
undergo a reduction in stability over time, which can result in
reduced mechanochromic properties. A reduction in mechanochromic
properties can be accompanied by an undesirable reduction in a
visually observable indication that the article in question has
undergone a threshold mechanical stress event.
[0005] It would be desirable to develop new mechanochromic
materials that can be used to provide a visually observable
indication that an article, which incorporates such mechanochromic
materials, has undergone a threshold mechanical stress event. It
would be additionally desirable that such newly developed
mechanochromic materials posses improved stability.
SUMMARY OF THE INVENTION
[0006] In accordance with the present invention, there is provided
a controlled radical polymerization initiator comprising at least
one radically transferable group, wherein the controlled radical
polymerization initiator comprises at least one of, (a) a
spirooxazine compound and (b) an indenonaphthopyran compound, that
each independently comprise at least one radically transferrable
group.
[0007] The spirooxazine compound is represented by the following
Formula (I),
##STR00003##
[0008] With reference to Formula (I), n is from 1 to 4, p is from 1
to 2, q is from 1 to 4, and R.sub.1 independently for each n,
R.sub.2 independently for each p, R.sub.3 independently for each q,
R.sub.4, R.sub.5, and R.sub.6 are each independently selected from
hydrogen, hydrocarbyl and substituted hydrocarbyl each optionally
interrupted with at least one of --O--, --S--, --C(O)--, --C(O)O,
--OC(O)O--, --S(O)--, --SO.sub.2--, --N(R.sup.11)--, and
--Si(R.sup.11)(R.sup.12)-- wherein R.sup.11 and R.sup.12 are each
independently selected from hydrogen, hydrocarbyl and substituted
hydrocarbyl, and combinations of two or more thereof.
[0009] The indenonaphthopyran is represented by the following
Formula (II),
##STR00004##
[0010] With reference to Formula (II), x is from 1 to 4, y is from
1 to 4, R.sub.7 independently for each x, R.sub.8 independently for
each y, R.sub.9, and R.sub.10 are each independently selected from
hydrogen, hydrocarbyl and substituted hydrocarbyl each optionally
interrupted with at least one of --O--, --S--, --C(O)--, --C(O)O--,
--OC(O)O--, --S(O)--, --SO.sub.2--, --N(R.sup.11)--, and
--Si(R.sup.11)(R.sup.12)-- wherein R.sup.11 and R.sup.12 are each
independently selected from hydrogen, hydrocarbyl and substituted
hydrocarbyl, and combinations of two or more thereof, and
[0011] With further reference to Formula (II), B and B' are each
independently selected from unsubstituted aryl, substituted aryl,
unsubstituted heteroaryl, substituted heteroaryl, and polyalkoxy,
or B and B' taken together form a ring structure selected from
unsubstituted fluoren-9-ylidene, substituted fluoren-9-ylidene,
saturated spiro-monocyclic hydrocarbon ring, saturated
spiro-bicyclic hydrocarbon ring, and spiro-tricyclic hydrocarbon
ring.
[0012] With further reference to the spirooxazine represented by
Formula (I), there is the proviso that at least one of R.sub.1
independently for each n, R.sub.2 independently for each p, R.sub.3
independently for each q, R.sub.4, R.sub.5, and R.sub.6,
independently comprise the radically transferable group.
[0013] With further reference to the indenonaphthopyran represented
by Formula (II), there is the proviso that at least one of R.sub.7
independently for each x, R.sub.8 independently for each y,
R.sub.9, R.sub.10, B, and B', independently comprise the radically
transferable group.
[0014] In accordance with the present invention, there is further
provided a polymer composition comprising at least one polymer
prepared by controlled radical polymerization initiated in the
presence of a controlled radical polymerization initiator having at
least one radically transferable group, wherein each polymer
prepared by controlled radical polymerization is independently
represented by the following Formula (V),
##STR00005##
[0015] With reference to Formula (V): M independently for each w is
a residue of a monomer; .phi. is a residue of the controlled
radical polymerization initiator that is free of the radically
transferable group; X, independently for each z, is or is derived
from the radically transferable group; w, independently for each z,
is an integer of at least 2; and z is an integer of at least 1.
[0016] The controlled radical polymerization initiator from which
the polymer represented by Formula (V) is prepared is selected from
(a) the spirooxazine compound represented by Formula (I) and/or (b)
the indenonaphthopyran represented by Formula (II) as described
above, and in each case as described in further detail herein.
[0017] The features that characterize the present invention are
pointed out with particularity in the claims, which are annexed to
and form a part of this disclosure. These and other features of the
invention, its operating advantages and the specific objects
obtained by its use will be more fully understood from the
following detailed description in which non-limiting embodiments of
the invention are illustrated and described.
DETAILED DESCRIPTION OF THE INVENTION
[0018] As used herein, the articles "a," "an," and "the" include
plural referents unless otherwise expressly and unequivocally
limited to one referent.
[0019] Unless otherwise indicated, all ranges or ratios disclosed
herein are to be understood to encompass any and all subranges or
subratios subsumed therein. For example, a stated range or ratio of
"1 to 10" should be considered to include any and all subranges
between (and inclusive of) the minimum value of 1 and the maximum
value of 10; that is, all subranges or subratios beginning with a
minimum value of 1 or more and ending with a maximum value of 10 or
less, such as but not limited to 1 to 6.1, 3.5 to 7.8, and 5.5 to
10.
[0020] As used herein, unless otherwise indicated, left-to-right
representations of linking groups, such as divalent linking groups,
are inclusive of other appropriate orientations, such as, but not
limited to, right-to-left orientations. For purposes of
non-limiting illustration, the left-to-right representation of the
divalent linking group
##STR00006##
or equivalently --C(O)O--, is inclusive of the right-to-left
representation thereof,
##STR00007##
or equivalently --O(O)C-- or --OC(O)--.
[0021] Other than in the operating examples, or where otherwise
indicated, all numbers expressing quantities of ingredients,
reaction conditions, and so forth used in the specification and
claims are to be understood as modified in all instances by the
term "about."
[0022] As used herein, molecular weight values of polymers, such as
weight average molecular weights (Mw) and number average molecular
weights (Mn), are determined by gel permeation chromatography using
appropriate standards, such as polystyrene standards.
[0023] As used herein, polydispersity index (PDI) values represent
a ratio of the weight average molecular weight (Mw) to the number
average molecular weight (Mn) of the polymer (i.e., Mw/Mn).
[0024] As used herein, the term "polymer" means homopolymers (e.g.,
prepared from a single monomer species), copolymers (e.g., prepared
from at least taro monomer species), and graft polymers.
[0025] As used herein, the term "(meth)acrylate" and similar terms,
such as "(meth)acrylic acid ester" means methacrylates and/or
acrylates. As used herein, the term "(meth)acrylic acid" means
methacrylic acid and/or acrylic acid.
[0026] As used herein, spatial or directional terms, such as
"left", "right", "inner", "outer", "above", "below", and the like,
relate to the invention as it is depicted in the drawing figures.
However, it is to be understood that, the invention can assume
various alternative orientations and, accordingly, such terms are
not to be considered as limiting.
[0027] As used herein, the terms "formed over," "deposited over,"
"provided over," "applied over," residing over," or "positioned
over," mean formed, deposited, provided, applied, residing, or
positioned on but not necessarily in direct (or abutting) contact
with the underlying element, or surface of the underlying element.
For example, a layer "positioned over" a substrate does not
preclude the presence of one or more other layers, coatings, or
films of the same or different composition located between the
positioned or formed layer and the substrate.
[0028] As used herein, the term "ring position" and related terms,
such as "ring positions," means a particular position in a ring
structure, such as the fused ring structure, of a chemical
compound, such as the spirooxazine compounds represented by Formula
(I) and the indenonaphthopyran compounds represented by Formula
(II), and which are depicted herein in accordance with some
embodiments by numbers within the ring structures of the related
representative chemical formulas.
[0029] All documents, such as but not limited to issued, patents
and patent applications, referred to herein, and unless otherwise
indicated, are to be considered to be "incorporated by reference"
their entirety.
[0030] As used herein, recitations of "linear or branched" groups,
such as linear or branched alkyl, are herein understood to include:
a methylene group or a methyl group; groups that are linear, such
as linear C.sub.2-C.sub.20 alkyl groups; and groups that are
appropriately branched, such as branched C.sub.3-C.sub.20 alkyl
groups.
[0031] As used herein the term "hydrocarbyl" and similar terms,
such as "hydrocarbyl substituent," means linear or branched
C.sub.1-C.sub.25 alkyl (e.g., linear or branched C.sub.1-C.sub.10
alkyl); linear or branched C.sub.2-25 alkenyl (e.g., linear or
branched C.sub.2-C.sub.10 alkenyl); linear or branched
C.sub.2-C.sub.25 alkynyl (e.g., linear or branched C.sub.2-C.sub.10
alkynyl); C.sub.3-C.sub.12 cycloalkyl (e.g., C.sub.3-C.sub.10
cycloalkyl); C.sub.3-C.sub.12 heterocycloalkyl (having at least one
hetero atom in the cyclic ring); C.sub.5-C.sub.18 aryl (including
polycyclic aryl groups) (e.g., C.sub.5-C.sub.10 aryl);
C.sub.5-C.sub.18 heteroaryl (having at least one hetero atom in the
aromatic ring); and C.sub.6-C.sub.24 aralkyl (e.g.,
C.sub.6-C.sub.10 aralkyl).
[0032] Representative alkyl groups include but are not limited to
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,
tort-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and
decyl. Representative alkenyl groups include but are not limited to
vinyl, allyl and propenyl. Representative alkynyl groups include
but are not limited to ethynyl, 1-propynyl, 2-propynyl, 1-butynyl,
and 2-butynyl. Representative cycloalkyl groups include but are not
limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and
cyclooctyl substituents. Representative heterocycloalkyl groups
include but are not limited to tetrahydrofuranyl, tetrahydropyranyl
and piperidinyl. Representative aryl groups include but are not
limited to phenyl, naphthyl, and triptycene. Representative
heteroaryl groups include but are not limited to furanyl, pyranyl
and pyridinyl. Representative aralkyl groups include but are not
limited to benzyl, and phenethyl.
[0033] The term "cycloalkyl" as used herein also includes: bridged
ring polycycloalkyl groups (or bridged ring polycyclic alkyl
groups), such as but not limited to, bicyclo[2.2.1]heptyl (or
norbornyl) and bicyclo[2.2.2]octyl; and fused ring polycycloalkyl
groups (or fused ring polycyclic alkyl groups), such as, but not
limited to, octahydro-1 indenyl, and decahydronaphthalenyl.
[0034] The term "substituted hydrocarbyl" as used herein means a
hydrocarbyl group in which at least one hydrogen thereof has been
substituted with a group that is other than hydrogen, such as, but
not limited to, halo groups, hydroxyl groups, ether groups, thiol
groups, thio ether groups, carboxylic acid groups, carboxylic acid
ester groups, phosphoric acid groups, phosphoric acid ester groups,
sulfonic acid groups, sulfonic acid ester groups, nitro groups,
cyano groups, hydrocarbyl groups (e.g., alkyl, alkenyl, alkynyl,
cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and aralkyl
groups), and amine groups, such as --N(R.sub.11')(R.sub.12') where
R.sub.11' and R.sub.12' are each independently selected from
hydrogen, hydrocarbyl and substituted hydrocarbyl.
[0035] The term "substituted hydrocarbyl" is inclusive of
halohydrocarbyl (or halo substituted hydrocarbyl) substituents. The
term "halohydrocarbyl" as used herein, and similar terms, such as
halo substituted hydrocarbyl, means that at least one hydrogen atom
of the hydrocarbyl (e.g., of the alkyl, alkenyl, alkynyl,
cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and aralkyl groups)
is replaced with a halogen atom selected from chlorine, bromine,
fluorine and iodine. The degree of halogenation can range from at
least one hydrogen atom but less than all hydrogen atoms being
replaced by a halogen atom (e.g., a fluoromethyl group), to full
halogenation (perhalogenation) in which all replaceable hydrogen
atoms on the hydrocarbyl group have each been replaced by a halogen
atom (e.g., trifluoromethyl or perfluoromethyl). Correspondingly,
the term "perhalohydrocarbyl group" as used herein means a
hydrocarbyl group in which all replaceable hydrogens have been
replaced with a halogen. Examples of perhalohydrocarbyl groups
include, but are not limited to, perhalogenated phenyl groups and
perhalogenated alkyl groups.
[0036] The hydrocarbyl and substituted hydrocarbyl groups from
which the various groups described herein can each be independently
selected, such as, but not limited to, R.sub.1-R.sub.10, R.sup.11,
R.sup.12, R.sub.13, and R.sub.14 can in each case be independently
and optionally interrupted with at least one of --O--, --S--,
--C(O)--, --C(O)O--, --OC(O)O--, --S(O)--, --SO.sub.2--,
--N(R.sup.11)-- and --Si(R.sup.11)(R.sup.12)--. As used herein, by
interrupted with at least one of --O--, --S--, --C(O)--, --C(O)O--,
--OC(O)O--, --S(O)--, --SO.sub.2--, --N(R.sup.11)--, and
--Si(R.sup.11)(R.sup.12)--, means that at least one carbon of, but
less than all of the carbons of, the hydrocarbyl group or
substituted hydrocarbyl group, is in each case independently
replaced with one of the recited divalent non-carbon linking
groups. The hydrocarbyl and substituted hydrocarbyl groups can be
interrupted with two or more of the above recited linking groups,
which can be adjacent to each other or separated by one or more
carbons. For purposes of non-limiting illustration, a combination
of adjacent --C(O)-- and --N(R.sup.11)-- can provide a divalent
amide linking or interrupting group, --C(O)--N(R.sup.11)--. For
purposes of further non-limiting illustration, a combination of
adjacent --N(R.sup.11)--, --C(O)-- and --O-- can provide a divalent
carbamate (or urethane) linking or interrupting group,
--N(R.sup.11)--C(O)--O--, where R.sup.11 is hydrogen.
[0037] As used herein, the term "mechanochromic" and similar terms,
such as "mechanochromic compound" means having an absorption
spectrum for at least visible radiation that varies in response to
mechanical stress. Further, as used herein the term "mechanochromic
material" means any substance that is adapted to display
mechanochromic properties (such as, adapted to have an absorption
spectrum for at least visible radiation that varies in response to
mechanical stress) and which includes at least one mechanochromic
compound, at least one polymer, and/or a polymer composition
according to the present invention.
[0038] The mechanochromic compounds, materials, polymers, polymer
compositions, and articles of the present invention are, with some
embodiments, capable of converting from a first state, for example
a "clear state" or a "colorless state" to a second state, for
example a "colored state," in response to mechanical stress. With
some embodiments of the present invention, the mechanochromic
compounds, materials, polymers, polymer compositions, and articles
of the present invention undergo minimal, or are substantially free
of, reversion back to the previous state (such as a clear or
colorless state) after exposure to and optional removal of the
mechanical stress.
[0039] As used herein to modify the term "state," the terms "first"
and "second" are not intended to refer to any particular order or
chronology, but instead refer to two different conditions or
properties. For purposes of non-limiting illustration, the first
state and the second state of a mechanochromic compounds, polymers,
polymer compositions, and articles of the present invention can
differ with respect to at least one optical property, such as but
not limited to the absorption of visible and/or UV radiation. Thus,
according to various non-limiting embodiments disclosed herein, the
mechanochromic compounds, polymers, polymer compositions, and
articles of the present invention can have a different absorption
spectrum in each of the first and second state. For example, while
not limiting herein, a mechanochromic compounds, polymers, polymer
compositions, and articles of the present invention can be clear in
the first state and colored in the second state. Alternatively,
mechanochromic compounds, polymers, polymer compositions, and
articles of the present invention can have a first color in the
first state and a second color in the second state.
[0040] As used herein, the term "actinic radiation" means
electromagnetic radiation that is capable of causing a response in
a material, such as, but not limited to, transforming a
photochromic material from one form or state to another state, or
initiating polymerization.
[0041] As used herein the term "film" means a pre-formed layer
having a generally uniform thickness that is not capable of
self-support.
[0042] As used herein the term "sheet" means a pre-formed layer
having a generally uniform thickness that is capable of
self-support.
[0043] As used herein the term "coating" means a supported film
derived from a flowable composition, which can have a uniform
thickness or non-uniform thickness, and specifically excludes
polymeric sheets and unsupported polymer films. A coating that
includes one or more mechanochromic polymers or compositions of the
present invention can, with some embodiments, be a mechanochromic
coating.
[0044] As used herein, the term controlled radical polymerization"
and related terms such as "controlled radical polymerization
method(s)" includes, but is not limited to, atom transfer radical
polymerization (ATRP), single electron transfer polymerization
(SETP), reversible addition-fragmentation chain transfer (RAFT),
and nitroxide-mediated polymerization (NMP).
[0045] Controlled radical polymerization, such as ATRP, is
described generally as a "living polymerization," i.e., a
chain-growth polymerization that propagates with essentially no
chain transfer and essentially no chain termination. The molecular
weight of a polymer prepared by controlled radical polymerization
can be controlled by the stoichiometry of the reactants, such as
the initial concentration of monomer(s) and initiator(s). In
addition, controlled radical polymerization also provides polymers
having characteristics including, but not limited to: narrow
molecular weight distributions, such as polydispersity index (PDI)
values less than 2.5; and/or well defined polymer chain structure,
such as block copolymers and alternating copolymers, with some
embodiments.
[0046] For purposes of non-limiting illustration of controlled
radical polymerization processes, the ATRP process is described in
further detail as follows. The ATRP process can be described
generally as including: polymerizing one or more radically
polymerizable monomers in the presence of an initiation system;
forming a polymer; and isolating the formed polymer. The initiation
system includes, with some embodiments: an initiator having at
least one radically transferable atom or group; a transition metal
compound, such as a catalyst, which participates in a reversible
redox cycle with the initiator; and a ligand, which coordinates
with the transition metal compound. The ATRP process is described
in further detail in U.S. Pat. Nos. 5,763,548, 5,789,487,
5,807,937, 6,538,091, 6,887,962, and 7,572,874. With some
embodiments, the polymers and polymer compositions of the present
invention prepared by controlled radical polymerization, are
prepared generally in accordance with the ATRP method disclosed at
column 4, line 12, through column 5, line 67 of U.S. Pat. No.
6,265,489, which disclosure is incorporated herein by
reference.
[0047] With some embodiments, there are provided controlled radical
polymerization initiators having at least one radically
transferable group, in which the controlled radical polymerization
initiators include at least one spirooxazine compound represented
by Formula (I), and/or at least one indenonaphthopyran compound
represented by Formula (II), as described previously herein.
[0048] The controlled radical polymerization initiators of the
present invention, with some embodiments, are each independently
mechanochromic controlled radical polymerization initiators. With
some further embodiments, polymers prepared from the controlled
radical polymerization initiators of the present invention are
mechanochromic polymers. In accordance with some additional
embodiments of the present invention, polymer compositions that
include the polymers of the present invention are mechanochromic
polymer composition. With some additional embodiments, articles
that include the polymers of the present invention are
mechanochromic articles.
[0049] The controlled radical polymerization initiators of the
present invention can, with some embodiments, each, independently
have at least one radically transferable group, such as from 1 to
20, or from 1 to 15, or from 1 to 10, or from 1 to 5, or from 1 to
4, or from 1 to 3, or 1 or 2 radically transferable groups. With
some further embodiments, the controlled radical polymerization
initiators of the present invention each independently have at
least 2 radically transferable groups, such as from 2 to 20, or
from 2 to 15, or from 2 to 10, or from 2 to 5, or from 2 to 4, or 2
or 3. With some embodiments, each controlled radical polymerization
initiator of the present invention independently has two (2)
radically transferable groups.
[0050] With some embodiments of the controlled radical
polymerization initiator of the present invention, and with further
reference to the spirooxazine represented by Formula (I), at least
two of, R.sub.1 independently for each n, R.sub.2 independently for
each p, R.sub.3 independently for each q, R.sub.4, R.sub.5, and
R.sub.6, independently comprise the radically transferable
group.
[0051] With some embodiments of the controlled radical
polymerization initiator of the present invention, and with further
reference to the indenonaphthopyran represented by Formula (II), at
least two of, R.sub.7 independently for each x, R.sub.8
independently for each y, R.sub.9, R.sub.10, B, and B',
independently comprise the radically transferable group.
[0052] The spirooxazine represented by Formula (I), with some
embodiments, includes at least one first radically transferable
group, and at least one second radically transferrable group. In
further accordance with some embodiments, for the spirooxazine
represented by Formula (I): at least one of R.sub.1 independently
for each n, and R.sub.2 independently for each p, independently
include the first radically transferable group; and at least one of
R.sub.3 independently for each q, R.sub.4, R.sub.5 and R.sub.6
independently comprise the second radically transferable group.
Each first radically transferable group and each second radically
transferable group can be the same or different.
[0053] While not intending to be bound by any theory, and with
reference to Formula (I), it is believed based on the evidence at
hand that the spirooxazine compound of the present invention, with
some embodiments, is converted from a first state (which can be
visibly non-colored) to a second state (which can be visibly
colored) when bond (a') between ring positions 3' and 4' is broken.
As such, and with some embodiments, when the spirooxazine
represented by Formula (I) includes at least one first radically
transferable group and at least one second radically transferrable
group, each first radically transferable group is positioned so as
to be on one side of the spirooxazine relative to bond (a') (at
least one R.sub.1 and/or at least one R.sub.2 each independently
including a first radically transferable group), and each second
radically transferable group is positioned so as to be on the other
side of the spirooxazine relative to bond (a') (at least one
R.sub.3, and/or R.sub.4, and/or R.sub.5, and/or R.sub.6 each
independently include a second radically transferable group).
[0054] The indenonaphthopyran represented by Formula (II), with
some embodiments, includes at least one first radically
transferable group, and at least one second radically transferrable
group. In further accordance with some embodiments, for the
indenonaphthopyran represented by Formula (II): at least one of B
and B' independently include the first radically transferable
group; and at least one of R.sub.7 independently for each x,
R.sub.8 independently for each y, R.sub.9 and R.sub.10
independently include the second radically transferable group. Each
first radically transferable group and each second radically
transferable group can be the same or different.
[0055] While not intending to be bound by any theory, and with
reference to Formula (II), it is believed based on the evidence at
hand that the indenonaphthopyran compound of the present invention,
with some embodiments, is converted from a first state (which can
be visibly non-colored) to a second state (which can be visibly
colored) when bond (a) between ring positions 3 and 4 is broken. As
such, and with some embodiments, when the indenonaphthopyran
represented by Formula (II) includes at least one first radically
transferable group and at least one second radically transferrable
group, each first radically transferable group is positioned so as
to be on one side of the indenonaphthopyran relative to bond (a) (B
and/or B' each independently including a first radically
transferable group), and each second radically transferable group
is positioned so as to be on the other side of the
indenonaphthopyran relative to bond (a) (at least one R.sub.7,
and/or at least one R.sub.8, and/or R.sub.9, and/or R.sub.10 each
independently include a second radically transferable group).
[0056] In accordance with some additional embodiments of the
present invention, the spirooxazino represented by Formula (I)
includes one first radically transferable group, and one second
radically transferrable group. In further accordance with some
embodiments, for the spirooxazine represented by Formula (I):
R.sub.1 or R.sub.2 includes the first radically transferable group:
and one of R.sub.3, R.sub.4, R.sub.5, and R.sub.6 includes the
second radically transferable group.
[0057] The indenonaphthopyran represented by Formula (II), with
some embodiments, includes one first radically transferable group,
and one second radically transferrable group. For the
indenonaphthopyran represented by Formula (II), and in accordance
with some embodiments: B or B' includes the first radically
transferable group; and one of R.sub.7, R.sub.8, R.sub.9, and
R.sub.10 includes the second radically transferable group.
[0058] The spirooxazine represented by Formula (I) includes, with
some further embodiments, one first radically transferable group,
and one second radically transferrable group. For the spirooxazine
represented by Formula (I), in accordance with some embodiments one
R.sub.2 includes the first radically transferable group; and one
R.sub.3 includes the second radically transferable group.
[0059] The indenonaphthopyran represented by Formula (II), with
some embodiments, includes one first radically transferable group,
and one second radically transferrable group. For the
indenonaphthopyran represented by Formula (II), and in accordance
with some embodiments: B or B' includes the first radically
transferable group, and one R.sub.7 or one R.sub.8 includes the
second radically transferable group.
[0060] Each radically transferable group of the controlled radical
polymerization initiators of the present invention can each be
independently selected from one or more atoms or groups that are
radically transferable under controlled radical polymerization
conditions. With some embodiments, each radically transferable
group is independently selected from Cl, Br, I, OR.sup.f, SR.sup.g,
SeR.sup.g, OC(.dbd.O)R.sup.g, OP(.dbd.O)R.sup.g,
OP(.dbd.O)(OR.sup.g).sub.2, OP(.dbd.O)OR.sup.g,
O--N(R.sup.g).sub.2, S--C(.dbd.S)N(R.sup.g).sub.2, CN, NC, SCN,
CNS, OCN, CNO, and N.sub.3. The Rf group (of OR.sup.f) is linear or
branched C.sub.1-C.sub.20 alkyl group, in which at least one
hydrogen group is optionally substituted with a halo group, such as
F or Cl). Each R.sup.g is independently selected from aryl or a
linear or branched C.sub.1-C.sub.20 alkyl group. With the
N(R.sup.g).sub.2 group, the R.sup.g groups can join to form a 5-,
6- or 7-membered heterocyclic ring.
[0061] With some further embodiments, each radically transferable
group of the controlled radical polymerization initiators of the
present invention are independently selected from Cl, Br, and I.
With some further embodiments, each radically transferable group of
the controlled radical polymerization initiators of the present
invention is Br.
[0062] For the spirooxazine represented by Formula (I), and in
accordance with some embodiments of the present invention, at least
one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6
independently include, or is, a group represented by the Formula
(III), and described in further detail below.
[0063] For the indenonaphthopyran represented by Formula (II), and
in accordance with some further embodiments of the present
invention, at least one of R.sub.7, R.sub.8, R.sub.9, R.sub.10, B,
and B' each independently include, or is, a group represented by
the following Formula (III):
##STR00008##
[0064] With reference to Formula (III), and independently for the
spirooxazine represented by Formula (I) and the indenonaphthopyran
represented by Formula (II), R.sub.13 is a divalent linking group
selected from a bond, a divalent hydrocarbyl group and a divalent
substituted hydrocarbyl group each optionally interrupted with at
least one of --O--, --S--, --C(O)--, --C(O)O--, OC(O)O--, --S(O)--,
--SO.sub.2--, --N(R.sup.15)-- and --Si(R.sup.15)(R.sup.16)-- and
combinations of two or more thereof. The R.sup.15 and R.sup.16
groups are in each case independently selected from hydrogen,
hydrocarbyl and substituted hydrocarbyl. With further reference to
Formula (III), R.sub.14 is a divalent linking group selected from a
bond, divalent hydrocarbyl, and divalent substituted hydrocarbyl,
and X is the radically transferrable group.
[0065] With some embodiments, and with further reference to Formula
(III), R.sub.13 is selected from a bond, divalent C.sub.1-C.sub.20
linear or branched alkyl, divalent C.sub.3-C.sub.10 cyclic alkyl,
divalent C.sub.3-C.sub.10 heterocyclic alkyl, divalent aryl,
divalent heteroaryl, and combinations thereof optionally
interrupted with at least one of --O-- and --S-- and combinations
of two or more thereof. With further reference to Formula (III),
and in accordance with some embodiments, R.sub.14 is selected from
divalent C.sub.1-C.sub.20 linear or branched alkyl, and X is
selected from a halo group.
[0066] With additional reference to Formula (III) and in accordance
with some embodiments, R.sub.13 is selected from a bond, divalent
C.sub.1-C.sub.10 linear or branched alkyl, divalent
C.sub.3-C.sub.10 heterocyclic alkyl, divalent aryl, and
combinations thereof optionally interrupted with at least one of
--O--. With further reference to Formula (III), and in accordance
with some embodiments, R.sub.14 is selected from divalent
C.sub.1-C.sub.10 linear or branched alkyl, and the halo group from
which X is selected is Cl, Br, or I.
[0067] With some embodiments, and with reference to Formula (III),
the divalent linking group R.sub.13 is bonded directly to the
spirooxazine represented by Formula (I). The divalent linking group
R.sub.13 of Formula (III) can, with some embodiments, be bonded to
another group that is bonded to the spirooxazine represented by
Formula (I), such as R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5,
and/or R.sub.6.
[0068] The divalent linking group R.sub.13 of the group represented
by Formula (III), with some embodiments, is bonded directly to the
indenonaphthopyran represented by Formula (II). The divalent
linking group R.sub.13 of Formula (III) can, with some embodiments,
be bonded to another group that is bonded to the indenonaphthopyran
represented by Formula (II), such as R.sub.7, R.sub.8, R.sub.9,
R.sub.10, B, and/or B'.
[0069] In accordance with some embodiments of the present
invention, for the spirooxazine represented by Formula (I), one
R.sub.2 independently includes, or is, the group represented by
Formula (III), and one R.sub.3 independently includes, or is, the
group represented by Formula (III).
[0070] With the spirooxazine represented by Formula (I), and with
some embodiments: one R.sub.2 independently includes, or is, the
group represented by Formula (III), which is bonded to ring
position 5' of the spirooxazine represented by Formula (I); one
R.sub.3 independently includes, or is, the group represented by
Formula (III), which bonded to ring position 5 of the spirooxazine
represented by Formula (I); and the remaining groups R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are free of the
group represented by Formula (III).
[0071] In accordance with some further embodiments of the present
invention, for the indenonaphthopyran represented by Formula (II),
one B or B' independently includes, or is, the group represented by
Formula (III), and one R.sub.7 or R.sub.8 independently includes,
or is, the group represented by Formula (III).
[0072] With the indenonaphthopyran represented by Formula (II), and
with some embodiments: one B or B at ring position 3 independently
includes, or is, the group represented by Formula (III); one
R.sub.8 independently includes, or is, the group represented by
Formula (III), which is bonded to ring position 11 of the
indenonaphthopyran represented by Formula (II); and the remaining
groups B or B', R.sub.7, R.sub.8, R.sub.9, and R.sub.10 are free of
the group represented by Formula (III).
[0073] With some embodiments, the group represented by Formula
(III) is selected from one or more groups represented by the
following Formulas (III-A) through (III-F):
##STR00009##
[0074] With reference to the above Formulas (III-A) through
(III-F), X in each case is independently a radically transferable
group, such as a halo group, such as Cl, Br, or I.
[0075] With the spirooxazine compound of the present invention as
represented by Formula (I), and in accordance with some
embodiments, R.sub.1 independently for each n and R.sub.2
independently for each p are each independently selected from
hydrogen, aryl, mono(C.sub.1-C.sub.6)alkoxyaryl,
di(C.sub.1-C.sub.6)alkoxyaryl, mono(C.sub.1-C.sub.6)alkylaryl,
di(C.sub.1-C.sub.6)alkylaryl, bromoaryl, chloroaryl, fluoroaryl,
C.sub.3-C.sub.7cycloalkylaryl, C.sub.3-C.sub.7 cycloalkyl,
C.sub.3-C.sub.7 cycloalkyloxy, C.sub.3-C.sub.7
cycloalkyloxy(C.sub.1-C.sub.6)alkyl, C.sub.3-C.sub.7
cycloalkyloxy(C.sub.1-C.sub.6)alkoxy, aryl(C.sub.1-C.sub.6)alkyl,
aryl(C.sub.1-C.sub.6)alkoxy, aryloxy,
aryloxy(C.sub.1-C.sub.6)alkyl, aryloxy(C.sub.1-C.sub.6)alkoxy,
mono- or di(C.sub.1-C.sub.6)alkylaryl(C.sub.1-C.sub.6)alkyl, mono-
or di(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub.6)alkyl, mono- or
di(C.sub.1-C.sub.6)alkylaryl(C.sub.1-C.sub.6)alkoxy, mono- or
di(C.sub.1-C.sub.6)alkoxyaryl(C.sub.1-C.sub.6)alkoxy, amino,
mono(C.sub.1-C.sub.6)alkylamino, di(C.sub.1-C.sub.6)alkylamino,
diarylamino, N--(C.sub.1-C.sub.8)alkylpiperazino, N-arylpiperazino,
aziridino, indolino, piperidino, arylpiperidino, morpholino,
thiamorpholino, tetrahydroquinolino, tetrahydroisoquinolino,
pyrryl, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.6 bromoalkyl,
C.sub.1-.sub.C6 chloroalkyl, C.sub.1-C.sub.6-fluoroalkyl,
C.sub.1-C.sub.6 alkoxy,
mono(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.4)alkyl, acryloxy,
methacryloxy, acyloxy(C.sub.1-C.sub.6 alkyl),
acyloxy(C.sub.3-C.sub.7 cycloalkyl), acyloxy(aryl), bromo, chloro
or fluoro.
[0076] In accordance with some embodiments of the present
invention, R.sub.3 of the spirooxazine represented by Formula (I)
is, independently for each q, chosen from hydrogen, C.sub.1-C.sub.5
alkyl, C.sub.1-C.sub.5 alkoxy, nitro, cyano, C.sub.1-C.sub.8
alkoxycarbonyl, acyloxy(C.sub.1-C.sub.6 alkyl),
acyloxy(C.sub.3-C.sub.7 cycloalkyl), acyloxy(aryl),, halo,
C.sub.1-C.sub.4 monohaloalkyl or C.sub.1-C.sub.4 polyhaloalkyl;
said halo substituents being chloro, fluoro, iodo or bromo.
[0077] In accordance with some further embodiments of the present
invention, R.sub.4 of the spirooxazine represented by Formula (I)
is chosen from hydrogen, C.sub.1-C.sub.8, alkyl, C.sub.3-C.sub.7
cycloalkyl, phen(C.sub.1-C.sub.4)alkyl,
naphth(C.sub.1-C.sub.4)alkyl, allyl,
acrylyloxy(C.sub.2-C.sub.6)alkyl,
methacrylyloxy(C.sub.2-C.sub.6)alkyl, C.sub.2-C.sub.4
acyloxy(C.sub.2-C.sub.6)alkyl, carboxy(C.sub.2-C.sub.6)alkyl,
cyano(C.sub.2-C.sub.6)alkyl, hydroxy(C.sub.2-C.sub.6)alkyl,
triarylsilyl, triarylsilyloxy, tri(C.sub.1-C.sub.6)alkylsilyl,
tri(C.sub.1-C.sub.6)alkylsilyloxy, tri(C.sub.1-C.sub.6)alkoxysilyl,
tri(C.sub.1-C.sub.6)alkoxysilyloxy,
di(C.sub.1-C.sub.6)alkyl(C.sub.1-C.sub.6 alkoxy)silyl,
di(C.sub.1-C.sub.6)alkyl(C.sub.1-C.sub.6alkoxy)silyloxy,
di(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6 alkyl)silyl,
di(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6 alkyl)silyloxy,
C.sub.1-C.sub.6 alkoxy(C.sub.2-C.sub.4)alkyl or
(C.sub.2H.sub.4O).sub.rCH.sub.3, wherein r is an integer from 1 to
6.
[0078] In accordance with some additional embodiments of the
present invention, R.sub.5 and R.sub.6 of the spirooxazine
represented by Formula (I) are each independently selected from
hydrogen, C.sub.1-C.sub.5 alkyl, acyloxy(C.sub.1-C.sub.6 alkyl),
acyloxy(C.sub.3-C.sub.7cycloalkyl), acyloxy(aryl), benzyl, phenyl,
mono- or di-substituted phenyl, said phenyl substituents being
C.sub.1-C.sub.5 alkyl or C.sub.1-C.sub.5 alkoxy; or R.sub.5 and
R.sub.6 taken together form a group chosen from a cyclic ring of
from 5 to 8 carbon atoms which includes the spiro carbon atom.
[0079] With the spirooxazine compound of the present invention as
represented by Formula (I), and in accordance with some
embodiments, R.sub.1 independently for each n and R.sub.2
independently for each p are each independently selected from
hydrogen, aryl, mono(C.sub.1-C.sub.6)alkoxyaryl,
di(C.sub.1-C.sub.6)alkylamino, piperidino, morpholino,
C.sub.1-C.sub.6 alkoxy, or fluoro.
[0080] in accordance with some embodiments of the present
invention, R.sub.3 of the spirooxazine represented by Formula (I)
is, independently for each q, selected from hydrogen,
C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy, C.sub.1-C.sub.8
alkoxycarbonyl, acyloxy(C.sub.1-C.sub.6 alkyl),
acyloxy(C.sub.3-C.sub.7 cycloalkyl), acyloxy(aryl),, halo,
C.sub.1-C.sub.4 monohaloalkyl or C.sub.1-C.sub.4 polyhaloalkyl; and
said halo substituents being chloro or fluoro.
[0081] In accordance with some further embodiments of the present
invention, R.sub.4 of the spirooxazine represented by Formula (I)
is selected from hydrogen, C.sub.1-C.sub.8 alkyl,
phen(C.sub.1-C.sub.4alkyl, acrylyloxy(C.sub.2-C.sub.6)alkyl,
methacrylyloxy(C.sub.2-C.sub.6)alkyl,
carboxy(C.sub.2-C.sub.6)alkyl, tri(C.sub.1-C.sub.6)alkylsilyloxy,
tri(C.sub.1-C.sub.6)alkoxysilyl,
tri(C.sub.1-C.sub.6)alkoxysilyloxy,
di(C.sub.1-C.sub.6)alkyl(C.sub.1-C.sub.6 alkoxy)silyl,
di(C.sub.1-C.sub.6)alkyl(C.sub.1-C.sub.6 alkoxy)silyloxy,
di(C.sub.1-C.sub.6)alkoxy(C.sub.1-C.sub.6 alkyl)silyl or
di(C.sub.1-C.sub.6)alkoxy(C.sub.r C.sub.6 alkyl)silyloxy,
[0082] In accordance with some additional embodiments of the
present invention, R.sub.5 and R.sub.6 of the spirooxazine
represented by Formula (I) are each independently selected from
hydrogen, C.sub.1-C.sub.5 alkyl, phenyl; or R.sub.5 and R.sub.6
taken together form a group chosen from a cyclic ring of from 5 to
8 carbon atoms which includes the spiro carbon atom.
[0083] For the indenonaphthopyran represented by Formula (II), and
in accordance with some embodiments, R.sub.7 independently for each
x and R.sub.8 independently for each y are each independently
selected from: hydrogen; a compatiblizing substituent; halogen
selected from fluoro and chloro; C.sub.1-C.sub.20 alkyl;
C.sub.3-C.sub.10 cycloalkyl; acyloxy(C.sub.1-C.sub.6 alkyl),
acyloxy(C.sub.3-C.sub.7 cycloalkyl), acyloxy(aryl); substituted or
unsubstituted phenyl, the phenyl substituents being selected from
hydroxyl, halogen, carbonyl, C.sub.1-C.sub.20 alkoxycarbonyl,
cyano, halo(C.sub.1-C.sub.20)alkyl, C.sub.1-C.sub.20 alkyl or
C.sub.1-C.sub.20 alkoxy; --O--R.sub.10' or --C(O)--R.sub.10' or
--C(O)--OR.sub.10', wherein R.sub.10' is hydrogen, C.sub.1-C.sub.20
alkyl, phenyl(C.sub.1-C.sub.20)alkyl, mono(C.sub.1-C.sub.20)alkyl
substituted phenyl(C.sub.1-C.sub.20)alkyl,
mono(C.sub.1-C.sub.20)alkoxy substituted
phenyl(C.sub.1-C.sub.20)alkyl,
(C.sub.1-C.sub.20)alkoxy(C.sub.2-C.sub.20)alkyl, C.sub.3-C.sub.10
cycloalkyl, or mono(C.sub.1-C.sub.20)alkyl substituted
C.sub.3-C.sub.10 cycloalkyl; --N(R.sub.11')R.sub.12', wherein
R.sub.11' and R.sub.12' are each independently hydrogen,
C.sub.1-C.sub.20 alkyl, phenyl, naphthyl, furanyl, benzofuran-2-yl,
benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl,
dibenzofuranyl, dibenzothienyl, benzopyridyl, fluorenyl,
C.sub.1-C.sub.20 alkylaryl, C.sub.3-C.sub.10 cycloalkyl,
C.sub.4-C.sub.20 bicycloalkyl, C.sub.5-C.sub.20 tricycloalkyl or
C.sub.1-C.sub.20 alkoxyalkyl, wherein said aryl group is phenyl or
naphthyl, or R.sub.11' and R.sub.12' come together with the
nitrogen atom to form a C.sub.3-C.sub.20 hetero-bicycloalkyl ring
or a C.sub.4-C.sub.20 hetero-tricycloalkyl ring.
[0084] For the indenonaphthopyran represented by Formula (II), and
in accordance with some further embodiments, R.sub.7 independently
for each x and R.sub.8 independently for each y are each
independently selected from a nitrogen containing ring represented
by the following graphic Formula (IVA),
##STR00010##
[0085] With reference to Formula (IVA), each --Y-- is independently
chosen for each occurrence from --CH.sub.2--, --CH(R.sub.13')--,
--C(R.sub.13).sub.2--, --CH(aryl)-, --C(aryl).sub.2-, and
--C(R.sub.13')(aryl)-, and Z is --Y--, --O--, --S--, --S(O)--,
--SO.sub.2--, --NH--, --N(R.sub.13')--, or --N(aryl)-, wherein each
R.sub.13' is independently C.sub.1-C.sub.20 alkyl, each aryl is
independently phenyl or naphthyl, m is an integer 1, 2 or 3, and p
is an integer 0, 1, 2, or 3 and provided that when p is 0, Z is
--Y--.
[0086] For the indenonaphthopyran represented by Formula (II), and
in accordance with some further embodiments, R.sub.7 independently
for each x and R.sub.8 independently for each y are each
independently selected from a group represented by one of the
following graphic Formulas (IVB) or (IVC):
##STR00011##
[0087] With reference to Formulas (IVB) and (IVC), R.sub.15,
R.sub.16, and R.sub.17 are each independently hydrogen,
C.sub.1-C.sub.6 alkyl, phenyl, or naphthyl, or the groups R.sub.15
and R.sub.16 together form a ring of 5 to 8 carbon atoms and each
R.sup.d is independently for each occurrence selected from
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, fluoro or chloro,
and Q is an integer 0, 1, 2, or 3.
[0088] For the indenonaphthopyran represented by Formula (II), and
in accordance with some additional embodiments, R.sub.7
independently for each x and R.sub.8 independently for each y are
each independently selected from unsubstituted, mono-, or
di-substituted C.sub.4-C.sub.18 spirobicyclic amine, or
unsubstituted, mono-, and di-substituted C.sub.4-C.sub.18
spirotricyclic amine, wherein said substituents are independently
aryl, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, or
phenyl(C.sub.1-C.sub.20)alkyl.
[0089] In accordance with some embodiments, and with further
reference to the indenonaphthopyran represented by Formula (II),
two adjacent R.sub.7 groups, or two adjacent R.sub.8 groups,
independently together form a group represented by one of the
following Formulas (IVD) and (IVE):
##STR00012##
[0090] With reference to Formulas (IVD) and (IVE), T and T' are
each independently oxygen or the group --NR.sub.11'--, where
R.sub.11', R.sub.15, and R.sub.16 are as set forth above.
[0091] In accordance with some further embodiments, and with
further reference to the indenonaphthopyran represented by Formula
(II), R.sub.9 and R.sub.10 are each independently selected from the
following classes of groups (i) through (v).
[0092] With some embodiments, R.sub.9 and R.sub.10 of Formula (II)
are each independently selected from, (i) hydrogen,
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 haloalkyl,
C.sub.3-C.sub.10 cycloalkyl, acyloxy(C.sub.1-C.sub.6 alkyl),
acyloxy(C.sub.3-C.sub.7 cycloalkyl), acyloxy(aryl), allyl, benzyl,
or mono-substituted benzyl, said benzyl substituents being chosen
from halogen, C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20
alkoxy.
[0093] With some embodiments, R.sub.9 and R.sub.10 of Formula (II)
are each independently selected from, (ii) an unsubstituted, mono-
di- or tri-substituted group chosen from phenyl, naphthyl,
phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl,
benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, or
indolyl, said group substituents in each case being independently
chosen from halogen, C.sub.1-C.sub.20 alkyl or C.sub.1-C.sub.20
alkoxy.
[0094] With some embodiments, R.sub.9 and R.sub.10 of Formula (II)
are each independently selected from, (iii) mono-substituted
phenyl, said substituent located at the pare position being
--(CH.sub.2).sub.t-- or --O--(CH.sub.2).sub.t--, wherein t is the
integer 1, 2, 3, 4, 5 or 6, said substituent being connected to an
aryl group which is a member of a photochromic material.
[0095] With some embodiments, R.sub.9 and R.sub.10 of Formula (II)
are each independently selected from, (iv) the group
--CH(R.sup.18)G, wherein R.sup.18 is hydrogen, C.sub.1-C.sub.6
alkyl or the unsubstituted, mono- or di-substituted aryl groups
phenyl or naphthyl, and G is --CH.sub.2OR.sup.19, wherein R.sup.19
is hydrogen, --C(O)R.sup.10, C.sub.1-C.sub.20 alkyl,
C.sub.1-C.sub.20 alkoxy(C.sub.1-C.sub.20)alkyl,
phenyl(C.sub.1-C.sub.20)alkyl, mono(C.sub.1-C.sub.20)alkoxy
substituted phenyl(C.sub.1-C.sub.20)alkyl, or the unsubstituted,
mono- or di-substituted aryl groups phenyl or naphthyl, each of
said phenyl and naphthyl group substituents being C.sub.1-C.sub.20
alkyl or C.sub.1-C.sub.20 alkoxy.
[0096] With some embodiments, (v) R.sub.9 and R.sub.10 together
form a spiro substituent selected from a substituted or
unsubstituted spiro-carbocyclic ring containing 3 to 6 carbon
atoms, a substituted or unsubstituted spiro-heterocyclic ring
containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including
the spirocarbon atom, said spiro-carbocyclic ring and
spiro-heterocyclic ring being annellated with 0, 1 or 2 benzene
rings, said substituents being hydrogen or C.sub.1-C.sub.20
alkyl.
[0097] In accordance with some additional embodiments, and with
further reference to the indenonaphthopyran represented by Formula
(I), B and B' are each independently: an aryl group that is
monosubstituted with a compatiblizing substituent; a substituted
phenyl; a substituted aryl; a substituted 9-julolindinyl; a
substituted heteroaromatic group chosen from pyridyl, furanyl,
benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,
benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl,
benzopyridyl, indolinyl, and fluorenyl, wherein the phenyl, aryl,
9-julolindinyl, or heteroaromatic substituent is a reactive
substituent R; an unsubstituted, mono-, di-, or tri-substituted
phenyl or aryl group; 9-julolidinyl; or an unsubstituted, mono- or
di-substituted heteroaromatic group chosen from pyridyl, furanyl,
benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,
benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl,
benzopyridyl, indolinyl, and fluorenyl.
[0098] The phenyl, aryl and heteroaromatic substituents, from which
B and B' can each be independently selected, are in each case
independently: hydroxyl, a group --C(.dbd.O)R.sub.21, wherein
R.sub.21 is --OR.sub.22, --N(R.sub.23)R.sub.24, piperidino, or
morpholino, wherein R.sub.22 is allyl, C.sub.1-C.sub.20 alkyl,
phenyl, mono(C.sub.1-C.sub.20)alkyl substituted phenyl,
mono(C.sub.1-C.sub.20)alkoxy substituted phenyl,
phenyl(C.sub.1-C.sub.20)alkyl, mono(C.sub.1-C.sub.20)alkyl
substituted phenyl(C.sub.1-C.sub.20)alkyl,
mono(C.sub.1-C.sub.20)alkoxy substituted
phenyl(C.sub.1-C.sub.20)alkyl, C.sub.1-C.sub.20
alkoxy(C.sub.2-C.sub.20)alkyl or C.sub.1-C.sub.20 haloalkyl,
R.sub.23 and R.sub.24 are each independently C.sub.1-C.sub.20
alkyl, C.sub.5-C.sub.10 cycloalkyl, phenyl or substituted phenyl,
the phenyl substituents being C.sub.1-C.sub.20 alkyl or
C.sub.1-C.sub.20 alkoxy, and said halo substituent is chloro or
fluoro, aryl, mono(C.sub.1-C.sub.20)alkoxyaryl,
di(C.sub.1-C.sub.20)alkoxyaryl, mono(C.sub.1-C.sub.20)alkylaryl,
di(C.sub.1-C.sub.20alkylaryl, haloaryl, C.sub.3-C.sub.10
cycloalkylaryl, C.sub.3-C.sub.10 cycloalkyl, C.sub.3-C.sub.10
cycloalkyloxy, C.sub.3-C.sub.10
cycloalkyloxy(C.sub.1-C.sub.20)alkyl, C.sub.3-C.sub.10
cycloalkyloxy(C.sub.1-C.sub.20)alkoxy, aryl(C.sub.1-C.sub.20)alkyl,
aryl(C.sub.1-C.sub.20)alkoxy, aryloxy,
aryloxy(C.sub.1-C.sub.20)alkyl, aryloxy(C.sub.1-C.sub.20)alkoxy,
mono- or di(C.sub.1-C.sub.20)alkylaryl(C.sub.1-C.sub.20)alkyl,
mono- or di-(C.sub.1-C.sub.20)alkoxyaryl(C.sub.1-C.sub.20)alkyl,
mono- or di-(C.sub.1-C.sub.20)alkylaryl(C.sub.1-C.sub.20)alkoxy,
mono- or di-(C.sub.1-C.sub.20)alkoxyaryl(C.sub.1-C.sub.20)alkoxy,
amino, mono- or di-(C.sub.1-C.sub.20)alkylamino, diarylamino,
piperazino, N--(C.sub.1-C.sub.20)alkylpiperazino, N-arylpiperazino,
aziridino, indolino, piperidino, morpholino, thiomorpholino,
tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl,
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 haloalkyl, alkoxy,
mono(C.sub.1-C.sub.20)alkoxy(C.sub.1-C.sub.20)alkyl, acryloxy,
methacryloxy, acyloxy(C.sub.1-C.sub.6 alkyl),
acyloxy(C.sub.3-C.sub.7 cycloalkyl), acyloxy(aryl), or halogen.
[0099] In accordance with some alternative embodiments, and with
further reference to the indenonaphthopyran represented by Formula
(II), B and B' are each independently an unsubstituted or
mono-substituted group chosen from pyrazolyl, imidazolyl,
pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl,
phenoxazinyl, phenazinyl, and acridinyl. Each of these substituents
are, with some embodiments, C.sub.1-C.sub.20 alkyl,
C.sub.1-C.sub.20 alkoxy, phenyl, or halogen.
[0100] In accordance with some alternative embodiments, and with
further reference to the indenonaphthopyran represented by Formula
(II), B and B' are each independently a group represented by one
of:
##STR00013##
[0101] With reference to the formulas immediately above, K is
--CH.sub.2-- or --O--, and M is --O-- or substituted nitrogen,
provided that when M is substituted nitrogen, K is --CH.sub.2--,
the substituted nitrogen substituents being hydrogen,
C.sub.1-C.sub.20 alkyl, or C.sub.1-C.sub.20 acyl, each R.sub.25
being independently chosen for each occurrence from
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, hydroxy, and
halogen, R.sub.26 and R.sub.27 each being independently hydrogen or
C.sub.1-C.sub.20 alkyl, and u is an integer ranging from 0 to
2.
[0102] In accordance with some alternative embodiments, and with
further reference to the indenonaphthopyran represented by Formula
(II), B and B' are each independently, a group represented by:
##STR00014##
[0103] With reference to the formula immediately above, R.sub.28 is
hydrogen or C.sub.1-C.sub.20 alkyl, and R.sub.29 is an
unsubstituted, mono-, or di-substituted group chosen from naphthyl,
phenyl, furanyl, and thienyl, in which the substituents are
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, or halogen.
[0104] In accordance with some embodiments, B and B', of Formula
(II), taken together form one of a fluoren-9-ylidene, mono-, or
di-substituted fluoren-9-ylidene, each of said fluoren-9-ylidene,
in which the substituents are each independently chosen from
C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkoxy, and halogen.
[0105] With some embodiments, R.sub.7 independently for each x and
R.sub.8 independently for each y, of the indenonaphthopyran
represented by Formula (II), are each independently selected from,
hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.7 cycloalkyl,
morpholino, morpholino substituted with C.sub.1-C.sub.8 linear or
branched alkyl, C.sub.1-C.sub.8 haloalkyl, fluoro, chloro, and
--O--R.sub.10'.
[0106] With some further embodiments, R.sub.9 and R.sub.10, of the
indenonaphthopyran represented by Formula (II), are each
independently selected from hydrogen, C.sub.1-C.sub.8 alkyl,
C.sub.1-C.sub.8 haloalkyl, and C.sub.3-C.sub.7 cycloalkyl, or
together form a spiro substituent selected from a substituted or
unsubstituted spiro-carbocyclic ring containing 3 to 6 carbon
atoms.
[0107] With some additional embodiments, B and B', of the
indenonaphthopyran represented by Formula (II), are each
independently selected from aryl, aryl substituted with
C.sub.1-C.sub.6 alkoxy, and aryl substituted with morpholino.
[0108] As previously discussed with regard to the
indenonaphthopyran represented by Formula (II): R.sub.7 and
R.sub.8, can each be independently selected from a compatibilizing
substituent; and B and B' can each be selected from an aryl group
that is mono-substituted with a compatibilizing substituent. If the
indenonaphthopyran includes multiple compatibilizing substituents,
each compatibilizing substituent can be independently chosen.
[0109] Each compatibilizing substituent can independently be
represented by one of the following:
TABLE-US-00001 -A'-D-E-G-J (XIII); -G-E-G-J (XVI); -D-E-G-J (XIX);
-A'-D-J (XIV); -D-G-J (XVII); -D-J (XX); -A'-G-J (XV); -G-J
(XVIII); and -A'-J (XXI).
[0110] With formulas (XIII) through (XXI), non-limiting examples of
groups that -A'- can represent according to various non-limiting
embodiments disclosed herein include --O--, --C(.dbd.O)--,
--CH.sub.2--, --OC(.dbd.O)-- and --NHC(.dbd.O)--, provided that if
-A'- represents --O--, -A'-forms at least one bond with -J.
[0111] Non-limiting examples of groups that -D- can represent
according to various non-limiting embodiments include a diamine
residue or a derivative thereof, wherein a first amino nitrogen of
said diamine residue can form a bond with -A'-, or a substituent or
an available position on the indeno-fused naphthopyran, and a
second amino nitrogen of said diamine residue can form a bond with
-E-, -G- or -J; and an amino alcohol residue or a derivative
thereof, wherein an amino nitrogen of said amino alcohol residue
can form a bond with -A'-, or a substituent or an available
position on the indeno-fused naphthopyran, and an alcohol oxygen of
said amino alcohol residue can form a band with -E-, -G- or -J.
Alternatively, according to various non-limiting embodiments
disclosed herein the amino nitrogen of the amino alcohol residue
can form a bond with -E-, -G- or -J, and the alcohol oxygen of the
amino alcohol residue can form a bond with -A'-, or a substituent
or an available position on the indenonaphthopyran.
[0112] Non-limiting examples of suitable diamine residues that -D-
can represent include an aliphatic diamine residue, a cyclo
aliphatic diamine residue, a diazacycloalkane residue, an azacyclo
aliphatic amine residue, a diazacrown ether residue, and an
aromatic diamine residue. More particular, illustrative and
non-limiting examples of diamine residues that can be used in
conjunction with various non-limiting embodiments disclosed herein
include the following:
##STR00015##
[0113] Non-limiting examples of suitable amino alcohol residues
that -D- can represent include an aliphatic amino alcohol residue,
a cyclo aliphatic amino alcohol residue, an azacyclo aliphatic
alcohol residue, a diazacyclo aliphatic alcohol residue and an
aromatic amine alcohol residue. More particular, illustrative and
non-limiting examples of amino alcohol residues that can be used in
conjunction with various non-limiting embodiments disclosed herein
include the following:
##STR00016##
[0114] With continued reference to formulas (XIII) through (XXI)
above, according to various non-limiting embodiments disclosed
herein, -E- can represent a dicarboxylic acid residue or a
derivative thereof, wherein a first carbonyl group of said
dicarboxylic acid residue can form a bond with -G- or -D-, and a
second carbonyl group of said dicarboxylic acid residue can form a
bond with -G-. Non-limiting examples of suitable dicarboxylic acid
residues that -E- can represent include an aliphatic dicarboxylic
acid residue, a cycloaliphatic dicarboxylic acid residue and an
aromatic dicarboxylic acid residue. More particular, illustrative
and non-limiting examples of dicarboxylic acid residues that can be
used in conjunction with various non-limiting embodiments disclosed
herein include the following:
##STR00017##
[0115] According to various non-limiting embodiments disclosed
herein, -G- can represent a group represented by the following
general formula,
--[(OC.sub.2H.sub.4).sub.x(OC.sub.3H.sub.6).sub.y(OC.sub.4H.sub.8).sub.z-
]--O--
in which x, y and z are each independently chosen and range from 0
to 50, and a sum of x, y, and z ranges from 1 to 50; a polyol
residue or a derivative thereof, wherein a first polyol oxygen of
said polyol residue can form a bond with -A'-, -D-, -E-, or a
substituent or an available position on the indeno-fused
naphthopyran, and a second polyol oxygen of said polyol can form a
bond with -E- or -J; or a combination thereof, wherein the first
polyol oxygen of the polyol residue forms a bond with a group
--[(OC.sub.2H.sub.4).sub.x(OC.sub.3H.sub.6).sub.y(OC.sub.4H.sub.8).-
sub.z]-- (i.e., to form the group
--[(OC.sub.2H.sub.4).sub.x(OC.sub.3H.sub.6).sub.y(OC.sub.4H.sub.8)]--O--)-
, and the second polyol oxygen forms a bond with -E- or -J.
Non-limiting examples of suitable polyol residues that -G- can
represent include an aliphatic polyol residue, a cyclo aliphatic
polyol residue and an aromatic polyol residue.
[0116] More particular, illustrative and non-limiting examples of
polyols from which the polyol residues that -G- can represent can
be formed according to various non-limiting embodiments disclosed
herein include (a) low molecular weight polyols having an average
molecular weight less than 500, such as, but not limited to, those
set forth in U.S. Pat. No. 6,555,028 at col. 4, lines 48-50, and
col. 4, line 55 to col. 6, line 5, which disclosure is hereby
specifically incorporated by reference herein; (b) polyester
polyols, such as, but not limited to, those set forth in U.S. Pat.
No. 6,555,028 at col. 5, lines 7-33, which disclosure is hereby
specifically incorporated by reference herein; (c) polyether
polyols, such as but not limited to those set forth in U.S. Pat.
No. 6,555,028 at col. 5, lines 34-50, which disclosure is hereby
specifically incorporated by reference herein; (d) amide-containing
polyols, such as, but not limited to, those set forth in U.S. Pat.
No. 6,555,028 at col. 5, lines 51-62, which disclosure is hereby
specifically incorporated by reference; (e) epoxy polyols, such as,
but not limited to, those set forth in U.S. Pat. No. 6,555,028 at
col. 5 line 63 to col. 6, line 3, which disclosure is hereby
specifically incorporated by reference herein; (f) polyhydric
polyvinyl alcohols, such as, but not limited to, those set forth in
U.S. Pat. No. 6,555,028 at col. 6, lines 4-12, which disclosure is
hereby specifically incorporated by reference herein; (g) urethane
polyols, such as, but not limited to those set forth in U.S. Pat.
No. 6,555,028 at col. 6, lines 13-43, which disclosure is hereby
specifically incorporated by reference herein; (h) polyacrylic
polyols, such as, but not limited to those set forth in U.S. Pat.
No. 6,555,028 at col. 6, lines 43 to col. 7, line 40, which
disclosure is hereby specifically incorporated by reference herein;
(i) polycarbonate polyols, such as, but not limited to, those set
forth in U.S. Pat. No. 6,555,028 at col. 7, lines 41-55, which
disclosure is hereby specifically incorporated by reference herein;
and (j) mixtures of such polyols.
[0117] With further reference to formulas (XIII) through (XXI),
according to various non-limiting embodiments disclosed herein, -J
can represent a group -K, wherein -K represents a group such as,
but not limited to, --CH.sub.2COOH, --CH(CH.sub.3)COOH,
--C(O)(CH.sub.2).sub.wCOOH, --C.sub.6H.sub.4SO.sub.3H,
--C.sub.5H.sub.10SO.sub.3H, --C.sub.4H.sub.6SO.sub.3H,
--C.sub.3H.sub.6SO.sub.3H, --C.sub.2H.sub.4SO.sub.3H and
--SO.sub.3H, wherein "w" ranges from 1 to 18. According to other
non-limiting embodiments -J can represent hydrogen that forms a
bond with an oxygen or a nitrogen of linking group to form a
reactive moiety such as --OH or --NH. For example, according to
various non-limiting embodiments disclosed herein, -J can represent
hydrogen, provided that if -J represents hydrogen, -J is bonded to
an oxygen of -D- or -G-, or a nitrogen of -D-.
[0118] According to still further non-limiting embodiments, -J can
represent a group -L or residue thereof, wherein -L can represent a
reactive moiety. For example, according to various non-limiting
embodiments disclosed herein -L can represent a group such as, but
not limited to, acryl, methacryl, crotyl,
2-(methacryloxy)ethylcarbamyl, 2-(methacryloxy)ethoxycarbonyl,
4-vinylphenyl, vinyl, 1-chlorovinyl or epoxy. As used herein, the
terms acryl, methacryl, crotyl, 2-(methacryloxy)ethylcarbamyl,
2-(methacryloxy)ethoxycarbonyl, 4-vinylphenyl, vinyl,
1-chlorovinyl, and epoxy refer to the following structures:
##STR00018##
[0119] As previously discussed, -G- can represent a residue of a
polyol, which is defined herein to include hydroxy-containing
carbohydrates, such as those set forth in U.S. Pat. No. 6,555,028
at col. 7, line 56 to col. 8, line 17, which disclosure is hereby
specifically incorporated by reference herein. The polyol residue
can be formed, for example and without limitation herein, by the
reaction of one or more of the polyol hydroxyl groups with a
precursor of -A'-, such as a carboxylic acid or a methylene halide,
a precursor of polyalkoxylated group, such as polyalkylene glycol,
or a hydroxyl substituent of the indenonaphthopyran. The polyol can
be represented by q-(OH).sub.a and the residue of the polyol can be
represented by the formula --O-q-(OH).sub.a-1, wherein q is the
backbone or main chain of the polyhydroxy compound and "a" is at
least 2.
[0120] Further, as discussed above, one or more of the polyol
oxygens of -G- can form a bond with -J (i.e., forming the group
-G-J). For example, although not limiting herein, wherein the
reactive and/or compatibilizing substituent comprises the group
-G-J, if -G- represents a polyol residue and -J represents a group
-K that contains a carboxyl terminating group, -G-J can be produced
by reacting one or more polyol hydroxyl groups to form the group -K
(for example as discussed with respect to Reactions B and C at col.
13, line 22 to col. 16, line 15 of U.S. Pat. No. 6,555,028, which
disclosure is hereby specifically incorporated by reference herein)
to produce a carboxylated polyol residue. Alternatively, if -J
represents a group -K that contains a sulfo or sulfono terminating
group, although not limiting herein, -G-J can be produced by acidic
condensation of one or more of the polyol hydroxyl groups with
HOC.sub.6H.sub.4SO.sub.3H; HOC.sub.5H.sub.10SO.sub.3H;
HOC.sub.4H.sub.8SO.sub.3H; HOC.sub.3H.sub.6SO.sub.3H;
HOC.sub.2H.sub.4SO.sub.3H; or H.sub.2SO.sub.4, respectively.
Further, although not limiting herein, if -G- represents a polyol
residue and -J represents a group -L chosen from acryl, methacryl,
2-(methacryloxy)ethylcarbamyl and epoxy, -L can be added by
condensation of the polyol residue with acryloyl chloride,
methacryloyl chloride, 2-isocyanatoethyl methacrylate or
epichlorohydrin, respectively.
[0121] Further non-limiting examples of reactive and/or
compatibilizing substituents are set forth in U.S. Pat. No.
6,555,028, at col. 3, line 45 to col. 4, line 26, and U.S. Pat. No.
6,113,814 at col. 3, lines 30-64, which disclosures are hereby
specifically incorporated by reference herein.
[0122] The spirooxazine compounds of the present invention can be
prepared by art-recognized methods. With some embodiments, the
spirooxazine compounds of the present invention can be synthesized
in general accordance with the description provided in U.S. Pat.
No. 6,019,914 at column 9, lines 7-48, which disclosure is
incorporated herein by reference.
[0123] With some embodiments, the spirooxazine compounds of the
present invention are prepared in accordance with the synthetic
descriptions provided in the examples further herein.
[0124] The indenonaphthopyran compounds of the present invention
can be prepared by art-recognized methods. With some embodiments,
the indenonaphthopyran compounds of the present invention can be
synthesized in general accordance with the description provided in
U.S. Pat. No. 6,296,785, at column 10, line 52 through column 29,
line 18, which disclosure is incorporated herein by reference. With
some further embodiments, the indenonaphthopyran compounds of the
present invention can be synthesized in general accordance with the
description provided in U.S. Pat. No. 7,527,754 B2 at column 13,
line 52 through column 14, line 62, which disclosure is
incorporated herein by reference. With some additional further
embodiments, the indenonaphthopyran compounds of the present
invention can be synthesized in general accordance with the
description provided in U.S. Pat. No. 5,645,767, at column 5, line
6 through column 11, line 31, which disclosure is incorporated
herein by reference.
[0125] With some embodiments, the indenonaphthopyran compounds of
the present invention are prepared in accordance with the synthetic
descriptions provided in the examples further herein.
[0126] The present invention also relates to a polymer composition
that includes at least one polymer prepared by controlled radical
polymerization initiated in the presence of a controlled radical
polymerization initiator having at least one radically transferable
group, in which each polymer prepared by controlled radical
polymerization is independently represented by Formula (V) as
described previously herein. As described previously herein, the
controlled radical polymerization initiator is selected from a
spirooxazine represented by Formula (I), and an indenonaphthopyran
represented by Formula (II), which are each as described previously
herein.
[0127] As discussed previously herein and for purposes of
non-limiting illustration of controlled radical polymerization
processes, the ATRP process can be described generally as
including: polymerizing one or more radically polymerizable
monomers in the presence of an initiation system; forming a
polymer; and isolating the formed polymer. The initiation system
includes, with some embodiments: an initiator having at least one
radically transferable atom or group; a transition metal compound,
such as a catalyst, which participates in a reversible redox cycle
with the initiator; and a ligand, which coordinates with the
transition metal compound.
[0128] The initiator, used to prepare the polymers of the polymer
compositions of the present invention, includes the spirooxazine
compound represented by Formula (I) and/or the indenonaphthopyran
compound represented by Formula (II), with some embodiments.
[0129] Catalysts that can be used with some embodiments in
preparing polymers, by controlled radical polymerization (such as
ATRP), include any transition metal compound that can participate
in a redox cycle with the initiator and the growing polymer chain.
With some embodiments, the transition metal compound is selected
such that it does not form direct carbon-metal bonds with the
polymer chain. Transition metal catalysts useful in the present
invention can be represented by the following Formula (VI),
TM.sup.n+X.sub.t (VI)
[0130] With reference to Formula (VI), TM represents the transition
metal, t is the formal charge on the transition metal having a
value of from 0 to 7, and X is a counterion or covalently bonded
component. Examples of the transition metal (TM) include, but are
not limited to, Cu, Fe, Au, Ag, Hg, Pd, Pt, Co, Mn, Ru, Mo, Nb and
Zn. Examples of X include, but are not limited to, halogen,
hydroxy, oxygen, C.sub.1-C.sub.6-aloxy, cyano, cyanato, thiocyanato
and azido. With some embodiments, the transition metal is Cu(I) and
X is a halogen, such as chloride. Accordingly, with some
embodiments, a class of transition metal catalysts are the copper
halides, such as Cu(I)Cl. With some embodiments the transition
metal catalyst contains a small amount, such as 1 mole percent, of
a redox conjugate, for example, Cu(II)Cl.sub.2 when Cu(I)Cl is
used.
[0131] Ligands that can be used in preparing the polymers of the
present invention, by controlled radical polymerization (such as
ATRP), include, but are not limited to compounds having one or more
nitrogen, oxygen, phosphorus and/or sulfur atoms, which can
coordinate to the transition metal catalyst compound, such as
through sigma and/or pi bonds. Classes of useful ligands, include
but are not limited to: unsubstituted and substituted pyridines and
bipyridines; porphyrins; cryptands; crown ethers, such as
18-crown-6; polyamines, such as ethylenediamine; glycols, such as
alkylene glycols, such as ethylene glycol; carbon monoxide; and
coordinating monomers, such as styrene, acrylonitrile and
hydroxyalkyl (meth)acrylates. With some embodiments, the ligand is
selected from one or more substituted bipyridines, such as
4,4'-dialkylbipyridyls.
[0132] In preparing the polymers of the present invention, by
controlled radical polymerization (such as ATRP), the amounts and
relative proportions of initiator, transition metal compound and
ligand are those for which ATRP is most effectively performed. The
amount of initiator used can vary widely and is typically present
in the reaction medium in a concentration of from 10.sup.-4
moles/liter (M) to 3 M, such as, from 10.sup.-3 M to 10.sup.-1 M.
As the molecular weight of the polymer can be directly related to
the relative concentrations of initiator and monomer(s), the molar
ratio of initiator to monomer can be an important factor in polymer
preparation, with some embodiments. The molar ratio of initiator to
monomer is, with some embodiments, within the range of 10.sup.-4:1
to 0.5:1, or 10.sup.-3:1 to 5.times.10.sup.-2:1.
[0133] In preparing the polymers of the present invention by
controlled radical polymerization, such as by ATRP, the molar ratio
of transition metal compound to initiator is, with some
embodiments, in the range of 10.sup.-4:1 to 10:1, or 0.1:1 to 5:1.
The molar ratio of ligand to transition metal compound is, with
some embodiments, within the range of 0.1:1 to 100:1, or 0.2:1 to
10:1.
[0134] With reference to Formula (V), subscript z is an integer of
at least 1, such as from 1 to 10, or 1 to 5, or from 1 to 4, or
from 1 to 3, or 1 or 2. Subscript z, with some embodiments, is at
least 2, such as from 2 to 10, or from 2 to 5, or from 2 to 4, or 2
or 3, or 2. With some embodiments, subscript z is equal to the
number of radically transferable groups present on the controlled
radical polymerization initiator.
[0135] With further reference to Formula (V), subscript w,
independently for each z, is an integer of at least 2, such as from
2 to 1000, or from 2 to 500, or from 2 to 300, or from 2 to 200, or
from 2 to 100, or from 2 to 50, or from 2 to 40, or from 2 to 30,
or from 2 to 25, or from 2 to 20, or from 2 to 10, or from 2 to
5.
[0136] With additional reference to Formula (V), X, independently
for each z, is or is derived from the radically transferable group
that was originally bonded to the controlled radical polymerization
initiator. With some embodiments, when the radically transferable
group(s) of the controlled radical polymerization initiator (such
as the spirooxazine compound represented by Formula (I) and the
indenonaphthopyran represented by Formula (II)) is a halo group,
such as Br, then X can be the radically transferable bromo group
(Br), with some embodiments.
[0137] The radically transferable group can, with some embodiments,
optionally be (a) removed, or (b) chemically converted to another
moiety. With either of (a) or (b), the symbol X is considered
herein to be derived from the radically transferable group of the
initiator. The radically transferable group can be removed by
substitution with a nucleophilic compound, such as an alkali metal
alkoxylate, with some embodiments. With some embodiments, the
method by which the radically transferable group is either removed
or chemically converted is relatively mild with regard to the
reactive functionality of the polymer. Many nucleophilic
substitution reactions can result in loss of reactive functionality
from the polymer. For purposes of non-limiting illustration, with
some embodiments the polymer has oxirane functionality, which can
be lost in the presence of a nucleophile, such as an alkali metal
alkoxylate.
[0138] With some embodiments of the present invention, when the
radically transferable group is a halogen, the halogen can be
removed by a mild dehalogenation reaction, which does not reduce
sensitive functionality of the polymer, if any (such as oxirane
functionality, with some embodiments). The reaction is typically
performed as a post-reaction after the polymer has been formed, and
in the presence of at least an ATRP catalyst. With some
embodiments, the dehalogenation post-reaction is performed in the
presence of both an ATRP catalyst and its associated ligand.
[0139] The mild dehalogenation reaction is performed by contacting
the halogen terminated polymer of the present invention with one or
more ethylenically unsaturated compounds, which are not readily
radically polymerizable under at least a portion of the spectrum of
conditions under which controlled radical polymerizations, such as
atom transfer radical polymerizations, are performed, hereinafter
referred to as "limited radically polymerizable ethylenically
unsaturated compounds" (LRPEU compound). As used herein, by
"halogen terminated" and similar terms is meant to be inclusive
also of pendent halogens, such as would be present in branched,
comb and star polymers.
[0140] Not intending to be bound by any theory, it is believed,
based on the evidence at hand, that the reaction between the
halogen terminated polymer and one or more LRPEU compounds results
inL (1) removal of the terminal halogen group; and (2) the addition
of at least one carbon-carbon double bond where the terminal
carbon-halogen bond is broken. The dehalogenation reaction is
typically conducted at a temperature in the range of 0.degree. C.
to 200.degree. C., or from 0.degree. C. to 160.degree. C., and a
pressure in the range of 0.1 to 100 atmospheres, or from 0.1 to 50
atmospheres, with some embodiments. The reaction is also typically
performed in less than 24 hours, such as between 1 and 8 hours.
While the LRPEU compound can be added in less than a stoichiometric
amount, it is typically added in at least a stoichiometric amount
relative to the moles of terminal halogen present in the polymer.
When added in excess of a stoichiometric amount, the LRPEU compound
is typically present in an amount of no greater than 5 mole
percent, such as 1 to 3 mole percent, in excess of the total moles
of terminal halogen, with some embodiments.
[0141] LRPEU compounds are described in further detail at column
12, line 15 through column 13, line 18 of U.S. Pat. No. 6,268,433
B1, which disclosure is incorporated herein by reference. With some
embodiments, the LRPEU is free of halogen groups. Examples of LRPEU
compounds include, but are not limited to, 1,1-dimethylethylene,
1,1-diphenylethylene, isopropenyl acetate, alpha-methyl styrene,
1,1-dialkoxy olefin and mixtures thereof. Additional examples of
LRPEU compounds include, but are not limited to, dimethyl itaconate
and diisobutene (2,4,4-trimethyl-1-pentene).
[0142] As discussed previously herein with reference to Formula
(V), M, independently for each w, is a residue of a monomer. More
particularly, M, independently for each w, is a residue of an
ethylenically unsaturated radically polymerizable monomer. As used
herein, the term "ethylenically unsaturated radically polymerizable
monomer" and similar terms includes, but are not limited to, vinyl
monomers, allylic monomers, olefins and other ethylenically
unsaturated monomers that are radically polymerizable.
[0143] Classes of vinyl monomers from which each M of Formula (V)
can be independently derived include, but are not limited to,
(meth)acrylates, vinyl aromatic monomers, vinyl halides, and vinyl
esters of carboxylic acids, each of which can, with some
embodiments, optionally include one or more functional groups
selected from hydroxyl groups, thiol groups, primary amine groups,
secondary amine groups, and oxirane groups. With some embodiments,
the (meth)acrylates are selected from at least one of: alkyl
(meth)acrylates having from 1 to 20 carbon atoms in the alkyl
group; and alkyl (meth)acrylates having from 1 to 20 carbon atoms
in the alkyl group, in which the alkyl group includes or is
substituted with one or more functional groups selected from
hydroxyl groups, thiol groups, primary amine groups, secondary
amine groups, and oxirane groups. Examples of alkyl (meth)acrylates
having from 1 to 20 carbon atoms in the alkyl group that can be
used include, but are not limited to, methyl (meth)acrylate, ethyl
(meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate,
butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl
(meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate,
isobornyl (meth)acrylate, cyclohexyl (meth)acrylate and
3,3,5-trimethylcyclohexyl (meth)acrylate, one or more of which can,
with some embodiments, optionally include in the alkyl group
thereof one or more functional groups selected from hydroxyl
groups, thiol groups, primary amine groups, secondary amine groups,
and oxirane groups.
[0144] Examples of oxirane functional monomers from which each M of
Formula (V) can be derived, with some embodiments, include, but are
not limited to, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl
(meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate and
allyl glycidyl ether. With some embodiments, oxirane functionality
can be incorporated into the polymer by post-reaction, such as by
preparing a hydroxyl functional precursor polymer and converting
the precursor polymer to an oxirane functional polymer by reacting
at least some of the hydroxyl groups with epichlorohydrin, in
accordance with art-recognized methods.
[0145] Examples of vinyl aromatic monomers from which each M of
Formula (V) can be independently derived include, but are not
limited to, styrene, p-chloromethylstyrene, divinyl benzene, vinyl
naphthalene and divinyl naphthalene. Vinyl halides from which each
M can be independently derived include, but are not limited to,
vinyl chloride and vinylidene fluoride. Vinyl esters of carboxylic
acids include, but are not limited to, vinyl acetate, vinyl
butyrate, vinyl 3,4-dimethoxybenzoate and vinyl benzoate.
[0146] As used herein, by "olefin" and like terms is meant
unsaturated aliphatic hydrocarbons having one or more double bonds,
such as obtained by cracking petroleum fractions. Examples of
olefins from which each M of Formula (V) can be independently
dervied include, but are not limited to, propylene, 1-butene,
1,3-butadiene, isobutylene and diisobutylene.
[0147] As used herein, by "allylic monomer(s)" is meant monomers
containing substituted and/or unsubstituted allylic functionality,
such as one or more radicals represented by the following Formula
(VII),
H.sub.2C.dbd.C(R.sup.1)--CH.sub.2-- (VII)
[0148] With reference to Formula (VII), R.sup.1 is hydrogen,
halogen or a C.sub.1 to C.sub.4 alkyl group. With some embodiments,
R.sup.1 is hydrogen or methyl and consequently Formula (VII)
represents an unsubstituted (meth)allyl radical. Examples of
allylic monomers include, but are not limited to: (meth)allyl
alcohol; (meth)allyl ethers, such as methyl (meth)allyl ether;
allyl esters of carboxylic acids, such as (meth)allyl acetate,
(meth)allyl butyrate, (meth)allyl 3,4-dimethoxybenzoate and
(meth)allyl benzoate.
[0149] Other ethylenically unsaturated radically polymerizable
monomers from which each M of Formula (V) can be independently
derived include, but are not limited to: cyclic anhydrides, such as
maleic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride and
itaconic anhydride; esters of acids that are unsaturated but do not
have alpha, beta-ethylenic unsaturation, such as methyl ester of
undecylenic acid; and diesters of ethylenically unsaturated dibasic
acids, such as diethyl maleate.
[0150] The polymers of the present invention can, with some
embodiments, have polymer architecture selected from linear
polymers, branched polymers, hyperbranched polymers, star polymers,
graft polymers and mixtures thereof. The form, or gross
architecture, of the polymer can be controlled by the choice of
initiator and monomers used in its preparation. Linear polymers can
be prepared by using initiators, such as represented by Formulas
(I) and (II), having one or two radically transferable groups.
Branched polymers can be prepared by using branching monomers, such
as monomers containing radically transferable groups or more than
one ethylenically unsaturated radically polymerizable group, such
as 2-(2-bromopropionoxy)ethyl acrylate, p-chloromethylstyrene and
diethyleneglycol bis(methacrylate). Hyperbranched polymers can be
prepared by increasing the amount of branching monomer used.
[0151] Star polymers can be prepared using initiators having three
or more radically transferable groups, such as represented by
Formulas (I) and (II). Star polymers can be prepared by
art-recognized core-arm or arm-core methods. In the core-arm
method, the star polymer is prepared by polymerizing monomers in
the presence of the polyfunctional initiator. Polymer chains, or
arms, of similar composition and architecture grow out from the
initiator core, in the core-arm method. With the arm-core method,
the arms are prepared separately from the core and can optionally
have different compositions, architecture, molecular weight and
polydispersity indices (PDI's). The arms can have different
equivalent weights (such as different active hydrogen equivalent
weights), and some can have no functionality. After the preparation
of the arms, they are attached to the core by art-recognized
methods, so as to result in the formation of a arm-core
polymer.
[0152] The polymers of the present invention prepared by controlled
radical polymerization can have, with some embodiments, a
functional equivalent weight of at least 100 grams/equivalent, or
at least 200 grams/equivalent. The functional equivalent weight of
the polymer is, with some embodiments, less than 10,000
grams/equivalent, or less than 5,000 grams/equivalent, or less than
1,000 grams/equivalent. The functional equivalent weight of the
polymers of the present invention prepared by controlled radical
polymerization can range between any combination of these values,
inclusive of the recited values, such as from 100 to 10,000
grams/equivalent, or from 200 to 5,000 grams/equivalent, or from
200 to 1,000 grams/equivalent, inclusive of the recited values. The
functionality (or functional groups) of the polymer can, with some
embodiments, be selected from hydroxyl groups, thiol groups,
primary amine groups, secondary amine groups, and oxirane
groups.
[0153] The number average molecular weight (Mn) of the polymers of
the present invention prepared by controlled radical polymerization
is with some embodiments at least 250, or at least 500, or at least
1,000, or at least 2,000. The polymers of the present invention
prepared by controlled radical polymerization also have, with some
embodiments, an Mn of less than 16,000, or less than 10,000, or
less than 5,000. The Mn of the polymers of the present invention
prepared by controlled radical polymerization can, with some
embodiments, range between any combination of these values,
inclusive of the recited values, such as from 250 to 16,000, or
from 500 to 10,000, or from 1,000 to 8,000, or from 2,000 to 7,000,
inclusive of the recited values.
[0154] Prior to use in the polymer compositions of the present
invention, the controlled radical polymerization (CRP) catalyst,
such as the ATRP transition metal catalyst, and its associated
ligand are, with some embodiments, separated or removed from the
polymer. The CRP catalyst, such as the ATRP catalyst is removed,
with some embodiments, prior to conversion of a precursor polymer
to a functional polymer. Removal of the ATRP catalyst is achieved,
with some embodiments, using known methods, including, for example,
adding a catalyst binding agent to the a mixture of the polymer,
solvent and catalyst, followed by filtering. Examples of suitable
catalyst binding agents include, but are not limited to, alumina,
silica, clay or combinations thereof. A mixture of the polymer,
solvent and ATRP catalyst can be passed through a bed of catalyst
binding agent, with some embodiments. Alternatively, the ATRP
catalyst can be oxidized in situ and retained in the polymer
polymer.
[0155] The polymers of the present invention can be prepared, with
some embodiments, in the absence of solvent, such as by a bulk
polymerization process. With some embodiments, the polymer is
prepared in the presence of a solvent, such as water and/or an
organic solvent. Classes of useful organic solvents include, but
are not limited to, esters of carboxylic acids, ethers, cyclic
ethers, C.sub.5-C.sub.10alkanes, C.sub.5-C.sub.8 cycloalkanes,
aromatic hydrocarbon solvents, halogenated hydrocarbon solvents,
amides, nitrites, sulfoxides, sulfones and mixtures thereof.
Supercritical solvents, such as CO.sub.2, C.sub.1-C.sub.4 alkanes
and fluorocarbons, can also be employed. With some embodiments
aromatic hydrocarbon solvents are used, such as xylene, and mixed
aromatic solvents such as those commercially available from Exxon
Chemical America under the trademark SOLVESSO.
[0156] With some embodiments of the polymer composition of the
present invention, and with further reference to Formula (V): z is
at least 2; and the spirooxazine represented by Formula (I)
includes at least one first radically transferable group, and at
least one second radically transferrable group, in which for the
spirooxazine represented by Formula (I) at least one of R.sub.1
independently for each n, and R.sub.2 independently for each p,
independently comprise said first radically transferable group, and
at least one of R.sub.3 independently for each q, R.sub.4, R.sub.5
and R.sub.6 independently comprise said second radically
transferable group. In addition, when z is at least 2, and with
some embodiments, the indenonaphthopyran represented by Formula
(II) includes at least one first radically transferable group, and
at least one second radically transferrable group, in which for the
indenonaphthopyran represented by Formula (II) at least one of B
and B' independently comprise said first radically transferable
group, and at least one of R.sub.7 independently for each x,
R.sub.8 independently for each y, R.sub.9 and R.sub.10
independently comprise said second radically transferable
group.
[0157] With some further embodiments of the polymer composition of
the present invention, and with further reference to Formula (V): z
is 2; and the spirooxazine represented by Formula (I) includes one
first radically transferable group, and one second radically
transferrable group, in which for the spirooxazine represented by
Formula (I) one R.sub.2 comprises said first radically transferable
group, and one R.sub.3 comprises said second radically transferable
group. In addition, when z is 2, and with some embodiments, the
indenonaphthopyran represented by Formula (II) includes one first
radically transferable group, and one second radically
transferrable group, in which for the indenonaphthopyran
represented by Formula (II) one of B and B' comprises said first
radically transferable group, and one R.sub.8 comprises said second
radically transferable group.
[0158] With some embodiments of the polymer composition of the
present invention, one or more groups of the spirooxazine
represented by Formula (I), such as R.sub.1, R.sub.2, R.sub.3,
R.sub.4, R.sub.5, and/or R.sub.6 include a group represented by
Formula (III), as described previously herein. With some additional
embodiments of the polymer composition of the present invention,
one or more groups of the indenonaphthopyran represented by Formula
(II), such as R.sub.7, R.sub.8, R.sub.9, R.sub.10, B, and/or B' in
each case independently include the group represented by the
Formula (III), as described previously herein. As discussed
previously herein, X of the group represented by Formula (III) can,
with some embodiments be a halo group, such as Cl, Br, and I.
[0159] Each polymer prepared by controlled radical polymerization
of the polymer composition of the present invention can
independently be a thermoplastic polymer or a curable polymer. When
the polymer is a curable polymer it has, with some embodiments, one
or more functional groups that are reactive with the (i) functional
groups of another material, such as a crosslinking agent, and/or
(ii) other functional groups on the same polymer.
[0160] Each polymer prepared by controlled radical polymerization
of the polymer composition of the present invention can
independently be a thermoplastic polymer or a curable polymer. When
the polymer prepared by controlled radical polymerization is a
curable polymer it has, with some embodiments, one or more
functional groups that are reactive with the (i) functional groups
of another material, such as a crosslinking agent, and/or (ii)
other functional groups on the same polymer prepared by controlled
radical polymerization.
[0161] In accordance with some embodiments of the polymer
composition of the present invention: the polymer prepared by
controlled radical polymerization includes at least one first
reactive group; and the polymer composition further includes at
least one crosslinking agent that includes at least two second
reactive groups that are reactive with and form covalent bonds with
the first reactive group(s) of the polymer prepared by controlled
radical polymerization.
[0162] In accordance with some embodiments of the polymer
composition of the present invention: the polymer, that is prepared
by controlled radical polymerization, includes at least one active
hydrogen group selected from hydroxyl, thiol, carboxylic acid,
primary amine, and secondary amine; and the polymer composition
further includes at least one crosslinking agent that includes at
least two functional groups selected from cyclic carboxylic acid
anhydrides, oxiranes, thiooxiranes, isocyanates, thioisocyanates,
cyclic carboxylic acid esters, cyclic amides, and cyclic
carbonates. With some further embodiments, the crosslinking agent
includes at least two functional groups selected from oxiranes,
thiooxiranes, isocyanates, thioisocyanates. The crosslinking agent,
in accordance with some additional embodiments, includes at least
two functional groups selected from oxiranes and isocyanates.
[0163] The crosslinking agent, with some embodiments, includes a
separate polymer according to the present invention that is
prepared by controlled radical polymerization, which includes at
least two functional groups selected from cyclic carboxylic acid
anhydrides, oxiranes, thiooxiranes, isocyanates, thioisocyanates,
cyclic carboxylic acid esters, cyclic amides, and cyclic
carbonates. The crosslinking agent polymer can be prepared in
accordance with the description provided previously herein, using a
spirooxazine represented by Formula (I) or an indenonaphthopyran
represented by Formula (II) as a controlled radical polymerization
initiator.
[0164] With some embodiments, the crosslinking agent is prepared by
controlled radical polymerization, but is not prepared using a
spirooxazine represented by Formula (I) or an indenonaphthopyran
represented by Formula (II) as a controlled radical polymerization
initiator. With some further embodiments, the crosslinking agent is
not prepared by controlled radical polymerization.
[0165] The polymers prepared by controlled radical polymerization,
with some further embodiments, include at least one, such as two or
more, radically polymerizable ethylenically unsaturated groups,
such as, but not limited to, (meth)acryloyl groups and allylic
groups. When the polymers of the present invention include
radically polymerizable ethylenically unsaturated groups, the
polymer compositions of the present invention can be cured by
exposure to actinic radiation in the presence of a suitable
initiator, such as a photopolymerization initiator, and an optional
crosslinking agent that has two or more radically polymerizable
ethylenically unsaturated groups, in accordance with art-recognized
methods. The allylic groups of the polymers according to the
present invention, with some embodiments, can be described with
reference to Formula (VII) previously herein.
[0166] Examples of isocyanate functional materials from which the
crosslinking agent can be selected, with some embodiments, include
but are not limited to, toluene-2,4-diisocyanate;
toluene-2,6-diisocyanate; diphenyl methane-4,4'-diisocyanate;
diphenyl methane-2,4'-diisocyanate; para-phenylene diisocyanate;
biphenyl diisocyanate; 3,3'-dimethyl-4,4'-diphenylene diisocyanate;
tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate;
2,2,4-trimethyl hexane-1,6-diisocyanate; lysine methyl ester
diisocyanate; bis(isocyanato ethyl)fumarate; isophorone
diisocyanate; ethylene diisocyanate; dodecane-1,12-diisocyanate;
cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate;
cyclohexane-1,4-diisocyanate; methyl cyclohexyl diisocyanate;
hexahydrotoluene-2,4-diisocyanate;
hexahydrotoluene-2,6-diisocyanate;
hexahydrophenylene-1,3-diisocyanate;
hexahydrophenylene-1,4-diisocyanate;
perhydrodiphenylmethane-2,4'-diisocyanate;
perhydrodiphenylmethane-4,4'-diisocyanate and mixtures thereof.
[0167] The polyisocyanate crosslinking agent can, with some
embodiments, be selected from polyisocyanates prepared from dimers
and trimers of diisocyante monomers. Dimers and trimers of
diisocyanate monomers can be prepared by art-recognized methods,
such as described in U.S. Pat. No. 5,777,061 at column 3, line 44
through column 4, line 40. Dimers and trimers of the above recited
diisocyanate monomers can contain linkages selected from the group
consisting of isocyanurate, uretdione, biuret, allophanate and
combinations thereof.
[0168] The isocyanate functional crosslinking agent can also be
selected from (i) polyisocyanate functional polymer having at least
two isocyanate groups, (ii) oligomeric polyisocyanate functional
adduct and mixtures thereof. The polyisocyanate functional polymer
and oligomeric polyisocyanate functional adduct can each contain
structural linkages selected from urethane, i.e., --NH--C(O)--O--,
thiourethane, i.e., --NH--C(O)--S--, urea, e.g., --NH--C(O)--NH--,
and combinations of these structural linkages. The polyisocyanate
polymer can be prepared, by art-recognized methods, from one or
more monomers having at least two reactive hydrogen groups, such as
thiol, hydroxy, primary amine and secondary amine groups, and one
or more monomers having two or more isocyanate groups. The molar
equivalent ratio of reactive hydrogen groups to isocyanate groups
is selected such that the resulting polymer has the desired end
groups, i.e., isocyanate groups. The number average molecular
weight (Mn) of the polyisocyanate-functional polymer is less than
20,000, such as from 1,000 and 10,000, with some embodiments.
[0169] With some embodiments of the present invention, the
polyisocyanate functional polymer is a polyisocyanate functional
polyurethane prepared from aliphatic diols and aliphatic
diisocyanates. Optionally, the polyisocyanate functional
polyurethane may be prepared using relatively small amounts of
monomers having three or more functional groups, such as triols
and/or tiisocyanates, to increase the functionality and branching
of the polyurethane, in accordance with art-recognized methods.
[0170] As used herein, by "oligomeric polyisocyanate functional
adduct" is meant a material that is substantially free of polymeric
chain extension. Oligomeric polyisocyanate functional adducts can
be prepared by art-recognized methods from, for example, a compound
containing three or more active hydrogen groups, such as
trimethylolpropane (TMP), and an isocyanate monomer, such as
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI),
in a molar ratio of 1:3, respectively. In the case of TMP and IPDI,
by employing art-recognized starved feed and/or dilute solution
synthesis techniques, an oligomeric adduct having an average
isocyanate functionality of 3 can be prepared ("TMP-31PDI").
[0171] Depending on the type of active hydrogen group containing
compound(s) used (e.g., polyols, polyamines and polythiols) the
oligomeric polyisocyanate functional adduct can contain structural
linkages selected from the urethane, thiourethane, urea and
combinations thereof, as described previously herein. The active
hydrogen group containing compound is aliphatic with some
embodiments, such as TMP, trishydroxyisocyanurate, pentaerythritol
and trimethylolpropane tris(mercaptoacetate). The isocyanate
monomer is, with some embodiments, a diisocyanate monomer and can
be selected from those described previously herein.
[0172] The isocyanate groups of the isocyanate functional
crosslinking agent can, with some embodiments, be capped or blocked
with a capping/blocking agent. After exposure to elevated
temperature, the capping/blocking agent separates from the
isocyanate functional material, allowing the free/unblocked
isocyanate groups thereof to react and form covalent bonds with the
active hydrogen groups of the polymer prepared by controlled
radical polymerization according to the present invention. After
unblocking or decapping from the polyisocyanate, the capping agent
can volatize out of the composition (prior to the composition
becoming vitrified) and/or remain in the composition, such as a
plasticizer. With some embodiments, it is desirable that the
capping agent not form bubbles in the composition and/or overly
plasticize the composition after decapping.
[0173] The capping groups of the capped polyisocyanate crosslinking
agent can be selected from, with some embodiments hydroxy
functional compounds, 1H-azoles, lactams, ketoximes and mixtures
thereof. Classes of hydroxy functional compounds include, but are
not limited to, aliphatic, cycloaliphatic, or aromatic alkyl
monoalcohols or phenolics. Specific examples of hydroxy functional
compounds useful as capping agents, include, but are not limited
to: lower aliphatic alcohols such as methanol, ethanol, and
n-butanol; cycloaliphatic alcohols such as cyclohexanol and
tetrahydrofuran; aromatic-alkyl alcohols, such as phenyl carbinol
and methylphenyl carbinol; and glycol ethers, e.g., ethylene glycol
butyl ether, diethylene glycol butyl ether, ethylene glycol methyl
ether and propylene glycol methyl ether. With some embodiments, the
hydroxy functional capping groups include the phenolics, examples
of which include, but are not limited to phenol itself and
substituted phenols, such as cresol, nitrophenol and p-hydroxy
methylbenzoate.
[0174] Examples of 1H-azoles that are useful as capping groups
include, but are not limited to 1H-imidazole, 1H-pyrazole,
1H-3,5-dimethylpyrazole, 1H-2,5-dimethyl pyrazole,
1H-1,2,3-triazole, 1H-1,2,3-benzotriazole, 1H-1,2,4-triazole,
1H-5-methyl-1,2,4-triazole, and 1H-3-amino-1,2,4-triazole.
[0175] Ketoximes useful as capping groups include those prepared
from aliphatic or cycloaliphatic ketones. Examples of ketoxime
capping groups include, but are limited to, 2-propanone oxime
(acetone oxime), 2-butanone oxime, 2-pentanone oxime, 3-pentanone
oxime, 3-methyl-2-butanone oxime, 4-methyl-2-pentanone oxime,
3,3-dimethyl-2-butanone oxime, 2-heptanone oxime, 3-heptanone
oxime, 4-heptanone oxime, 5-methyl-3-heptanone oxime,
2,6-dimethyl-4-heptanone oxime, cyclopentanone oxime, cyclohexanone
oxime, 3-methylcyclohexanone oxime, 3,3,5-trimethylcyclohexanone
oxime and 3,5,5-trimethyl-2-cyclohexene-5-one oxime.
[0176] Examples of lactam capping groups include, but are not
limited to, e-caprolactam and 2-pyrrolidinone. Other suitable
capping groups include, morpholine, 3-aminopropyl morpholine and
N-hydroxy phthalimide.
[0177] Oxirane functional crosslinking agents can be prepared by
reacting a hydroxyl functional material having at least two
hydroxyl groups with a 2-(halomethyl)oxirane, such as
2-(chloromethyl)oxirane, which is also referred to as
epichlorohydrin. Examples of polyols that can be used to prepare
oxirane functional crosslinking agents include, but are not limited
to, glycerin, trimethylolpropane, trimethylolethane,
trishydroxyethylisocyanurate, pentaerythritol, ethylene glycol,
propylene glycol, trimethylene glycol, butanediol, heptanediol,
hexanediol, octanediol, 4,4'-(propane-2,2-diyl)dicyclohexanol,
4,4'-methylenedicyclohexanol, neopentyl glycol,
2,2,3-trimethylpentane-1,3-diol, 1,4-dimethylolcyclohexane,
2,2,4-trimethylpentane diol, 4,4'-(propane-2,2-diyl)diphenol, and
4,4'-methylenediphenol.
[0178] The oxirane functional crosslinking agent can be a polymeric
material. With some embodiments, the polymeric oxirane functional
crosslinking agent can be prepared from an oxirane functional
material having at least two oxirane groups and an active hydrogen
functional material having at least two active hydrogen groups,
such as at least two hydroxyl groups. Examples of polyols that can
be used to prepare polymeric oxirane functional crosslinking agents
include, but are not limited to those classes and examples recited
previously herein with regard to preparing the oxirane functional
crosslinking agent.
[0179] The polymer prepared by controlled radical polymerization,
with some embodiments, is present in the polymer composition of the
present invention in an amount of at least 2 percent by weight, or
at least 10 percent by weight, or at least 20 percent by weight, or
at least 30 percent by weight, or at least 50 percent by weight, or
at least 70 percent by weight, or at least 80 percent by weight,
based on total weight of resin solids of the polymer composition.
The polymer composition also, with some embodiments, contains the
polymer prepared by controlled radical polymerization in an amount
of less than or equal to 98 percent by weight, or less than or
equal to 95 by weight, or less than or equal to 90 percent by
weight, based on total weight of resin solids of the polymer
composition. The polymer prepared by controlled radical
polymerization can, with some embodiments, be present in the
polymer composition of the present invention in an amount ranging
between any combination of these values, inclusive of the recited
values, such as from 2 to 98 percent by weight, or from 10 to 98
percent by weight, or from 20 to 98 percent by weight, or from 30
to 98 percent by weight, or from 50 to 98 percent by weight, or
from 70 to 95 percent by weight, or from 80 to 90 percent by
weight, in each case based on total weight of resin solids of the
polymer composition. With some further embodiments, the polymer
prepared by controlled radical polymerization is present in the
polymer composition of the present invention in an amount of from
20 to 50 percent by weight, or from 5 to 30 percent by weight, or
from 10 to 25 percent by weight, in each case based on total weight
of resin solids of the polymer composition.
[0180] The crosslinking agent is present, with some embodiments, in
the polymer composition of the present invention in an amount of at
least 2 percent by weight, or at least 5 percent by weight, or at
least 10 percent by weight, based on total weight of resin solids
of the polymer composition. The crosslinking agent can also, with
some embodiments be present in the polymer composition in an amount
of less than or equal to 70 percent by weight, or an amount of less
than or equal to 50 percent by weight, or less than or equal to 30
percent by weight, or less than or equal to 20 percent by weight,
based on total weight of resin solids of the polymer composition.
The crosslinking agent can be present in the polymer composition of
the present invention in an amount ranging between any combination
of these values, inclusive of the recited values, such as from 2 to
70 percent by weight, or from 2 to 50 percent by weight, or from 5
to 30 percent by weight, or from 10 to 20 percent by weight, based
on total weight of resin solids of the curable particulate
composition, and , inclusive of the recited values.
[0181] The polymer prepared by controlled radical polymerization is
present in the polymer composition, with some embodiments, in an
amount of from 30 to 98 percent by weight, based on total resin
solids weight of the polymer composition; and the crosslinking
agent is present in the polymer composition, with some embodiments,
in an amount of from 2 to 70 percent by weight, based on total
resin solids weight of the polymer composition.
[0182] In accordance with some embodiments, the polymer
compositions of the present invention include one or more
additional polymers that do not include (and are free of) a residue
of a mechanochromic compound, such as represented by Formulas (I)
and (II), which can be referred to as non-mechanochromic polymers.
Examples of such non-mechanochromic polymers include, but are not
limited to, polyester polymers, polyurethane polymers,
polycarbonate polymers, polyether polymers, polyamide polymers,
polyimide polymers, polyamideimide polymers, polyurea polymers,
polysulfone polymers, polyketone polymers, polyvinyl polymers,
polyolefins, poly(meth)acrylates, and combinations of two or more
thereof. Each non-mechanochromic polymer can include, with some
embodiments: one or more (such as two or more) active hydrogen
groups, such as hydroxyl, thiol, carboxylic acid, primary amine,
and secondary amine; and/or one or more (such as two or more)
functional groups that are reactive with active hydrogen groups,
such as, cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes,
isocyanates, thioisocyanates, cyclic carboxylic acid esters, cyclic
amides, and cyclic carbonates. With some embodiments, the
non-mechanochromic polymer is present in an amount of from 2 to 98
percent by weight, or from 10 to 80 percent by weight, or from 20
to 70 percent by weight, or from 30 to 60 percent by weight, or
from 30 to 50 percent by weight, where the percent by weights are
in each case based on the total weight of the polymer of the
present invention (which includes a residue of a mechanochromic
compound such as represented by Formulas (I) and (II)) and the
non-mechanochromic polymer.
[0183] To achieve a suitable level of cure with the polymer
composition of the present invention, the equivalent ratio of
active hydrogen equivalents of the polymer prepared by controlled
radical polymerization, to isocyanate or oxirane equivalents of the
crosslinking agent is, with some embodiments, from 0.7:1 to 2:1, or
from 0.8:1 to 1.3:1.
[0184] The polymer composition of the present invention can be
cured by any suitable methods. With some embodiments, the polymer
composition is thermosetting, and is curable by exposure to
elevated temperature. As used herein, by "cured" is meant a three
dimensional crosslink network formed by covalent bond formation,
such as between the active hydrogen groups of the polymer prepared
by controlled radical polymerization and the isocyanate or oxirane
groups of the crosslinking agent. The temperature at which the
thermosetting polymer composition of the present invention is cured
is variable and depends in part on the amount of time during which
curing is conducted. With some embodiments, the thermosetting
polymer composition is cured at a temperature within the range of
90.degree. C. to 204.degree. C., or from 149.degree. C. to
204.degree. C., or from 154.degree. C. to 177.degree. C., for a
period of 20 to 60 minutes.
[0185] The polymer compositions of the present invention can also,
with some embodiments, include pigments and fillers. Examples of
pigments include, but are not limited to: inorganic pigments, such
as titanium dioxide and iron oxides; organic pigments, such as
phthalocyanines, anthraquinones, quinacridones and thioindigos; and
carbon blacks. Examples of fillers include, but are not limited to:
silica, such as precipitated silicas; clay; and barium sulfate.
When used in the polymer compositions of the present invention,
pigments and fillers can, with some embodiments, be present in
amounts of from 0.1 percent to 70 percent by weight, based on the
total solids weight of the polymer composition (excluding
solvent).
[0186] The polymer compositions of the present invention can, with
some embodiments, optionally contain additives such as, but not
limited to: waxes for flow and wetting; flow control agents, such
as poly(2-ethylhexyl)acrylate; antioxidants; and ultraviolet (UV)
light absorbers. Examples of useful antioxidants and UV light
absorbers include, but are not limited to, those available
commercially from BASF under the trademarks IRGANOX and TINUVIN.
These optional additives, when used, can be present in amounts up
to 20 percent by weight, based on total solids weight of the
polymer composition (excluding solvent).
[0187] The polymer compositions of the present can, with some
embodiments, include solvents, selected from water, organic
solvents, and combinations thereof.
[0188] Classes of organic solvents that can be present in the
polymer compositions of the present invention include, but are not
limited to: alcohols, e.g., methanol, ethanol, n-propanol,
iso-propanol, n-butanol, sec-butyl alcohol, tert-butyl alcohol,
iso-butyl alcohol, furfuryl alcohol and tetrahydrofurfuryl alcohol;
ketones or ketoalcohols, e.g., acetone, methyl ethyl ketone, and
diacetone alcohol; ethers, e.g., dimethyl ether and methyl ethyl
ether; cyclic ethers, e.g., tetrahydrofuran and dioxane; esters,
e.g., ethyl acetate, ethyl lactate, ethylene carbonate and
propylene carbonate; polyhydric alcohols, e.g., ethylene glycol,
diethylene glycol, triethylene glycol, propylene glycol,
tetraethylene glycol, polyethylene glycol, glycerol.
2-methyl-2,4-pentanediol and 1,2,6-hexantriol; hydroxy functional
ethers of alkylene glycols, e.g., butyl 2-hydroxyethyl ether, hexyl
2-hydroxyethyl ether, methyl 2-hydroxypropyl ether and phenyl
2-hydroxypropyl ether; nitrogen containing cyclic compounds, e.g.,
pyrrolidone, N-methyl-2-pyrrolidone and
1,3-dimethyl-2-imidazolidinone; and sulfur containing compounds
-such as thioglycol, dimethyl sulfoxide and tetramethylene
sulfone.
[0189] Solvent(s) can be present in the polymer compositions of the
present invention, in an amount of at least 5 percent by weight, or
at least 15 percent by weight, or at least 30 percent by weight,
based on the total weight of the polymer composition. The
solvent(s) can also be present in the polymer composition in an
amount of less than 95 percent by weight, or less than 80 percent
by weight, or less than 60 percent by weight, based on the total
weight of the pigment dispersion. The amount of solvent present in
the polymer composition can range between any combination of these
values, inclusive of the recited values, with some embodiments,
such as from 5 to 95 percent by weight, or from 15 to 80 percent by
weight, or from 30 to 60 percent by weight, in each case based on
the total weight of the polymer composition.
[0190] With some embodiments, the polymer composition includes an
additive selected from heat stabilizers, light stabilizers, and
combinations thereof. Examples of useful heat stabilizers and light
absorbers include, but are not limited to, those available
commercially from BASF under the trademarks IRGANOX and TINUVIN.
The optional heat stabilizers and light stabilizers, when used, can
be present in amounts up to 20 percent by weight, based on total
solids weight of the polymer composition (excluding solvent).
[0191] The present invention also relates to mechanochromic
articles that include the polymer composition of the present
invention as described previously herein. With some embodiments,
the mechanochromic article is selected from films, sheets, and
3-dimensional articles.
[0192] The 3-dimensional articles from which the mechanochromic
articles of the present invention can be selected include, but are
not limited to, ophthalmic articles, display articles, windows,
mirrors, protective articles and support articles.
[0193] The mechanochromic articles of the present invention, with
some embodiments, are selected from ophthalmic articles, and the
ophthalmic articles are selected from corrective lenses,
non-corrective lenses, contact lenses, and magnifying lenses. As
used herein the term "ophthalmic" means pertaining to or associated
with the eye and vision. Non-limiting examples of ophthalmic
articles or elements include corrective and non-corrective lenses,
including single vision or multi-vision lenses, which can be either
segmented or non-segmented multi-vision lenses (such as, but not
limited to, bifocal lenses, trifocal lenses and progressive
lenses), as well as other elements used to correct, protect, or
enhance (cosmetically or otherwise) vision, including without
limitation, contact lenses, intra-ocular lenses, magnifying lenses,
and protective lenses or visors.
[0194] The mechanochromic articles of the present invention, with
some embodiments, are selected from display articles, and the
display articles are selected from screens, monitors, and security
elements. As used herein the term "display" means the visible or
machine-readable representation of information in words, numbers,
symbols, designs or drawings. Non-limiting examples of display
articles, elements and devices include screens, monitors, and
security elements, such as security marks.
[0195] The mechanochromic articles of the present invention, with
some embodiments, are selected from protective articles, and the
protective articles are selected from protective lenses, protective
visors, protective headgear, and protective housings. Examples of
protective lenses include, but are not limited to, safety glasses
and safety goggles, such as used in a laboratory and/or a work
shop, such as a metal shop, welding shop, wood-working shop,
automotive shop/garage, and the like. Examples of protective visors
include, but are not limited to, those used with racing helmets
(such as automotive, motorcycle, and boat racing helmets), aircraft
helmets, hockey helmets, metal working helmets, and helmets used by
ground military personnel. Examples of protective headgear include,
but are not limited to, motorcycle helmets, aircraft helmets, speed
boat helmets, automotive race helmets, baseball helmets, hockey
helmets, equestrian helmets, helmets used by ground military
personnel, construction helmets, oil filed helmets, and helmets
used by metal workers. Examples of protective housings include, but
are not limited to, housings for sensitive equipment, such as,
analytical equipment, guidance systems (such as missile guidance
systems), and medical equipment (such as insulin pumps).
[0196] The mechanochromic articles of the present invention are,
with some embodiments, selected from support articles, and the
support articles are selected from rods, beams, crossarms, and
combinations thereof. The rods, beams, and crossarms can be
substantially unitary articles, or composed of a plurality of
components, in which at least some of the components are the
mechanochromic articles of the present invention.
[0197] The mechanochromic article of the present invention, with
some embodiments, is selected from a 3-dimensional article, and the
3-dimensionsal article includes a layer residing over at least a
portion of at least one surface of the 3-dimensional article, in
which the layer includes the polymer composition of the present
invention as described previously herein, and is a mechanochromic
layer. The mechanochromic layer can be selected from films, sheets,
and/or coatings.
[0198] The mechanochromic article of the present invention, with
some embodiments, is selected from a 3-dimensional article, and the
3-dimensionsal article includes a coating residing over at least a
portion of at least one surface of the 3-dimensional article, in
which the coating includes the polymer composition of the present
invention as described previously herein, and is a mechanochromic
coating.
[0199] With some embodiments, the coating is the polymer
composition of the present invention, and the coating is a
mechanochromic coating. The coating can be a single layer coating
or a multiple layer coating, in which each layer thereof can have
the same or a different composition. With some embodiments the
coating is a multiple layer coating that includes a primer over at
least a portion of a surface of the 3-dimensional article, a
mechanochromic layer formed over the primer layer (in which the
mechanochromic layer includes the polymer composition of the
present invention), and an optional clear layer formed over the
mechanochromic layer. The mechanochromic layer can be pigmented or
unpigmented, with some embodiments. With some embodiments, the
optional clear layer, which resides over the mechanochromic layer,
can include an additive selected from heat stabilizers and/or light
stabilizers. The heat stabilizers and light stabilizers can be
present in amount(s) and the thickness of the clear layer can be
selected such that photochromic activation of the residue of the
controlled radical polymerization initiator (represented by Formula
(I) and/or (II), which resides within the polymer backbone of the
polymer of the present invention) by actinic radiation is at least
minimized, or substantially eliminated. With some embodiments, and
for purposes of non-limiting illustration, the heat stabilizers and
light stabilizers can be present in the clear layer in a total
amount of up to 40% by weight, based on the total solids weight of
the clear layer.
[0200] There is also provided a mechanochromic article that
includes the polymer composition of the present invention, in which
the mechanochromic article further includes a coating residing over
at least a portion of at least one surface of the mechanochromic
article. The coating is free of the polymer composition of the
present invention, and the coating includes an additive selected
from heat stabilizers, light stabilizers, and combinations thereof.
The coating residing over the mechanochromic article can be
referred to as an overcoating. The overcoating, which resides over
the mechanochromic article, can be a clear overcoating, with some
embodiments of the present invention. The heat stabilizers and
light stabilizers can be present in amount(s) and the thickness of
the clear overcoating can be selected such that photochromic
activation of the residue of the controlled radical polymerization
initiator (represented by Formula (I) and/or (II), which resides
within the polymer backbone of the polymer of the present
invention) by actinic radiation is at least minimized, or
substantially eliminated. With some embodiments, and for purposes
of non-limiting illustration, the heat stabilizers and light
stabilizers can be present in the clear overcoating in a total
amount of up to 40% by weight, based on the total solids weight of
the clear overcoat.
[0201] The present invention is more particularly described in the
following examples, which are intended to be illustrative only,
since numerous modifications and variations therein will be
apparent to those skilled in the art. Unless otherwise specified,
all parts and percentages are by weight.
EXAMPLES
[0202] The examples of Part 1 describe the synthesis of controlled
radical polymerization initiators. Part 2 describes the preparation
of polymers made by controlled radical polymerization using the
initiators of Part 1.
Part 1. Preparation of Controlled Radical Polymizeration
Initiators
Example 1
##STR00019##
[0204] Into a 2 oz jar flushed with Nitrogen was added
3-phenyl-3-(4-(2-hydroxyethoxyphenyl))-6,7-dimethoxy-13-ethyl-13-(2-hydro-
xyethoxy)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran (0.56
g, 1 equiv), triethylamine (0.28 g, 3.1 equiv), and dichloromethane
(10.2 g). This mixture was cooled in a dry ice/ethanol bath, and a
solution of 2-bromopropionyl bromide (0.58 g, 3 equiv) in
dichloromethane (1.5 g) was added. The jar was resealed and allowed
to warm to room temperature. After stirring for 18 hours, 10 mL of
water was added. The layers were separated, and the aqueous layer
was extracted three times with dichloromethane. The combined
organic layers were washed with saturated sodium bicarbonate, dried
over MgSO.sub.4, and concentrated under vacuum. The residue was
filtered through a plug of silica, eluting with dichloromethane.
After concentration of the eluent, 0.83 g of a brown oil was
obtained, which was consistent with
3-phenyl-3-(4-(2-(2-bromopropionato)ethoxyphenyl))-6,7-dimethoxy-13-ethyl-
-13-(2-bromopropionatoethoxy)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]-
pyran by .sup.1H and .sup.13C NMR.
Example 2
##STR00020##
[0206] A solution of 1-nitroso-2,3-dihydroxynaphthalene, (1.08 g)
in 13.75 mL of 1,2-dichloroethane was charged to a round bottomed
flask and warmed to reflux. A mixture of
5-hydroxy-1,2,3,3-tetramethyl-3H-indol-1-ium iodide (1.74 g) and
triethylamine (1.15 g) was added dropwise. The resulting dark
solution was refluxed for 1 hour, then cooled to room temperature
and a blue product was collected via filtration. This was
immediately placed into a Nitrogen-flushed 2 oz jar. To the jar was
added triethylamine (2.88 g), and dichloromethane (6.5 mL). This
mixture was cooled in a dry ice/ethanol bath, and a solution of
2-bromoisobutyryl bromide (3.94 g) in dichloromethane (1.5 mL) was
added. The jar was resealed and allowed to warm to room
temperature. After stirring for 2 hours, the residue was dry packed
onto a 6 inch by 3/4 inch silica plug and eluted with 500 mL of a
2:1 solution of dichloromethane:heptanes, increasing to 5:1
dichloromethane:heptanes. The filtrate was concentrated, then the
residue was purified by column chromatography with an elution
gradient of 1:1 dichloromethane:heptanes, up to 4:1
dichloromethane:heptanes on silica, to provide
1,3,3-trimethylspiro[indoline-2,3'-naphtho[2,1-b][1,4]oxazine]-5,5'-diyl
bis(2-bromo-2-methylpropionate) as a dark brown solid which was
photochromic upon exposure to UV irradiation.
Example 3
##STR00021##
[0208] Into a 20 mL scintillation vial was charged
3-(4-methoxyphenyl)-3-(4-(2-hydroxyethoxyphenyl))-6,7-dimethoxy-11-carbox-
y-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran
(0.1323 g), dicyclohexylcarbodiimide (DCC, 0.044 g), ethylene
glycol (0.57 g), dimethylaminopyridine (0.0013 g), and
dichloromethane (3.2 mL) The resulting solution was stirred at room
temperature for 3 hours, at which time TLC analysis (100% ethyl
acetate) on silica gel indicated complete consumption of starting
material. The reaction was partitioned between dichloromethane and
water, and the layers were separated. The organic layer was washed
with water, dried over sodium sulfate and concentrated, yielding a
green solid. This material was then converted to the initiator
according to the general procedure in example 2, using 0.19 g of
bromoisobutyryl bromide, 0.103 g triethylamine and 3 mL of
dichloromethane (1.5 mL). Purification via column chromatography
(methylene chloride, silica gel) yielded 0.11 g of a photochromic
compound consistent with
3-(4-methoxyphenyl)-3-(4-(2-bromo-2-methylpropionato)ethoxyphenyl))-6,7-d-
imethoxy-11-(2-bromo-2-methylpropionatoethoxyoxyl)-13,13-dimethyl-3,13-dih-
ydro-indeno[2',3':3,4]naphtho[1,2-b]pyran by .sup.1H and .sup.13C
NMR.
Example 4
##STR00022##
[0210]
3-(4-2-hydroxyethoxyphenyl)-3-(4-methoxyphenyl)-6-methoxy-7-(3-hydr-
oxymethyl)piperidin-1-yl)-13,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]nap-
htho[1,2-b]pyran (0.038 g) was placed into a Nitrogen-flushed 2 oz
jar. To the jar was added triethylamine (0.028 g), and
dichloromethane (1 g). This mixture was cooled in a dry ice/ethanol
bath, and 2-bromoisobutyryl bromide (0.05 g,) in dichloromethane (1
g) was added. The jar was resealed and allowed to warm to room
temperature. After stirring overnight, the reaction was diluted
with 4 mL of water. The layers were separated, and the aqueous
layer was extracted three times with dichloromethane. The combined
organics were dried over MgSO.sub.4, and concentrated under vacuum.
The residue purified by column chromatography (silica gel) using an
elution gradient from 100% cyclohexane to 1:1 cyclohexane:diethyl
ether. After concentration of the eluent, 13.4 mg of
3-(4-(2-bromo-2-methylpropionylethoxyphenyl)-3-(4-methoxyphenyl)-6-methox-
y-7-(3-(2-bromo-2-methylpropionyloxymethyl)piperidin-1-yl)-13,13-dimethyl--
3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran was obtained as a
photochromic solid.
Example 5
##STR00023##
[0212]
3-(4-(3-hydroxymethylpiperidin-1-yl))-3-phenyl-6-methoxy-7-(3-hydro-
xymethyl)piperidin-1-yl)-11-bromo-13,13-dimethyl-3,13-dihydro-indeno[2',3'-
:3,4]naphtho[1,2-b]pyran (0.1 g) was placed into a Nitrogen-flushed
25 mL round bottomed flask. To the flask was added dichloromethane
(1.5 g), then the mixture was cooled in an ice water bath.
Triethylamine (0.0647 g) was added, followed by 2-bromoisobutyryl
bromide (0.088 g,). The flask was allowed to warm to room
temperature. After stirring overnight, the solvent was removed and
the residue was redissolved in diethyl ether. The salts were
removed via filtration, and the eluent was concentrated. The
residue was filtered through a short silica column to provide
3-(4-(3-(2-bromo-2-methylpropionyloxymethyl)piperidin-1-yl))-3-phenyl-6-m-
ethoxy-7-(3-(2-bromo-2-methylpropionyloxymethyl)piperidin-1-yl)-11-bromo-1-
3,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran
(0.116 g, 84%) as a bluish-black photochromic solid.
Part 2. Preparation of Polymer Dyes by Controlled Radical
Polymerization
Example 6
[0213] Into a flask immersed in a room temperature water bath was
placed the initiator
3-phenyl-3-(4-(2-(2-bromopropionato)ethoxyphenyl))-6,7-dimethoxy-13-ethyl-
-13-(2-bromopropionatoethoxy)-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]-
pyran of Example 1 (0.1 g, 1 equiv). Cu metal (0.03 g, 4 equivs),
tris(2-dimethylaminoethyl)amine (0.1 g, 4 equivs), and dry DMSO
(10.7 mL). The resulting mixture was purged with dry Nitrogen for
20 min. Methyl acrylate (21.3 g, 2500 equivs) was filtered through
a plug of alumina, purged with Nitrogen for 20 minutes, then added
to the flask. The mixture was allowed to stir overnight at room
temperature, after which a significant increase in viscosity was
observed. The material was dissolved in tetrahydrofuran (THF, 20.7
g) and stirred open to the atmosphere for 5 minutes, at which time
the viscous solution was filtered. The polymer was purified by
precipitation into methanol. The off-white polymer was collected
and dried under vacuum. The resulting polymeric compound was found
to be reversibly photochromic under UV irradiation.
Example 7
[0214] Into a flask immersed in a room temperature water bath was
placed the initiator
1,3,3-trimethylspiro[indoline-2,3'-naphtho[2,1-b][1,4]oxazine]-5,5'-diyl
bis(2-bromo-2-methylpropionate) of Example 2 (0.5 g, 1 equiv). Cu
metal (0.029 g, 2 equivs), tris(2-dimethylaminoethyl)amine (0.79 g,
2 equivs), and dry butyl acetate (1.3 mL). The resulting mixture
was purged with dry Nitrogen for 20 min. Methyl acrylate (0.73, 37
equiv) and hydroxypropyl acrylate (0.96 g, 33 equiv) were then
added to the flask. The mixture was allowed to stir overnight at
room temperature, after which a significant increase in viscosity
was observed. The material was dissolved in THF (20.7 g) then
filtered through a plug of glass wool. To the filtrate was added
approximately 2 g of AMBERLITE.RTM. IRC-748 (an ion exchange resin
available from Dow Chemical) and 4 drops of acetic acid. This was
stirred for 1 h, then filtered and concentrated to yield a thick
oil. .sup.1H NMR was consistent with the expected polymerization
product containing the residue of the initiator of Example 1. The
resulting polymeric material was found to be reversibly
photochromic under UV irradiation.
Example 8
[0215] The initiator
3-(4-methoxyphenyl)-3-(4-(2-bromo-2-methylpropionato)ethoxyphenyl))-6,7-d-
imethoxy-11-(2-bromo-2-methylpropionatoethoxyoxyl)-13,13-dimethyl-3,13-dih-
ydro-indeno[2',3':3,4]naphtho[1,2-b]pyran of Example 3 (0.0305 g)
was subjected to the conditions described in Example 6 except that
0.008 g Cu, 0.029 g tris(2-dimethylaminoethyl)amine, 4.32 g of
methyl acrylate, and 2.8 g of DMSO was used. Gel Permeation
Chromatography in THF indicated a peak MW of 128,614 (theory
140,000) relative to a linear polystyrene standard.
Example 9
[0216] The initiator
3-(4-(2-bromo-2-methylpropionylethoxyphenyl)-3-(4-methoxyphenyl)-6-methox-
y-7-(3-(2-bromo-2-methylpropionyloxymethyl)piperidin-1-yl)-13,13-dimethyl--
3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran of Example 4
(13.4 mg) was subjected to the polymerization conditions described
in Example 6 except that 0.0035 g Cu, 0.013 g
tris(2-dimethylaminoethyl)amine, 1.9 g of methyl acrylate, and 1.2
g of DMSO was used. Gel Permeation Chromatography in THF indicated
a peak MW of 163569 (theory 140,000) relative to a linear
polystyrene standard.
Example 10
[0217] The initiator
1,3,3-trimethylspiro[indoline-2,3'-naphtho[2,1-b][1,4]oxazine]-5,5'-diyl
bis(2-bromo-2-methylpropionate) of Example 2 (24.4 mg) was
subjected to the polymerization conditions described in Example 6
except that 0.0094 g Cu, 0.034 g tris(2-dimethylaminoethyl)amine,
5.19 g of methyl acrylate, and 3.4 g of DMSO was used. Gel
Permeation Chromatography in THF indicated a peak MW of 183811
(theory 140,000) relative to a linear polystyrene standard.
Example 11
[0218] The initiator
3-(4-(3-(2-bromo-2-methylpropionyloxymethyl)piperidin-1-yl))-3-phenyl-6-m-
ethoxy-7-(3-(2-bromo-2-methylpropionyloxymethyl)piperidin-1-yl)-11-bromo-1-
3,13-dimethyl-3,13-dihydro-indeno[2',3':3,4]naphtho[1,2-b]pyran of
Example 5 (0.0815 g) was placed into a flask immersed in a room
temperature water. To this was added Cu powder (0.0096 g),
tris(2-dimethylaminoethyl)amine (0.027 g), and dry butyl acetate
(1.0 mL). The resulting mixture was purged with dry Nitrogen for 10
minutes. Methyl acrylate (0.24) and hydroxypropyl acrylate (0.242
g) were then added to the flask. The mixture was allowed to stir
overnight at room temperature, after which no significant increase
in viscosity was observed. The mixture was then heated to
70.degree. C. and stirred for six hours, then cooled and stirred
overnight. The resulting material was dissolved in THF (10 mL) then
filtered through a plug of glass wool. To the filtrate was added
approximately 2 g of AMBERLITE IRC-748 resin and 4 drops of acetic
acid. This was stirred for 1 h, then filtered and concentrated to
yield a thick oil. The resulting material was found to be
reversibly photochromic under UV irradiation.
[0219] The present invention has been described with reference to
specific details of particular embodiments thereof. It is not
intended that such details be regarded as limitations upon the
scope of the invention except insofar as and to the extent that
they are included in the accompanying claims.
* * * * *